US10497881B2 - Organic semiconductor element, manufacturing method thereof, composition for forming organic semiconductor film, compound, and organic semiconductor film - Google Patents

Organic semiconductor element, manufacturing method thereof, composition for forming organic semiconductor film, compound, and organic semiconductor film Download PDF

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US10497881B2
US10497881B2 US15/497,239 US201715497239A US10497881B2 US 10497881 B2 US10497881 B2 US 10497881B2 US 201715497239 A US201715497239 A US 201715497239A US 10497881 B2 US10497881 B2 US 10497881B2
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Yuki HIRAI
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Fujifilm Corp
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    • H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene
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    • C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
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    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
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    • H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
    • H01L29/68—Types of semiconductor device ; Multistep manufacturing processes therefor controllable by only the electric current supplied, or only the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched
    • H01L29/76—Unipolar devices, e.g. field effect transistors
    • H01L29/772—Field effect transistors
    • H01L29/78—Field effect transistors with field effect produced by an insulated gate
    • H01L29/786—Thin film transistors, i.e. transistors with a channel being at least partly a thin film
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    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
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    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6574—Polycyclic condensed heteroaromatic hydrocarbons comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes
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    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
    • H10K10/40—Organic transistors
    • H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
    • H10K10/462—Insulated gate field-effect transistors [IGFETs]
    • H10K10/464—Lateral top-gate IGFETs comprising only a single gate
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    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
    • H10K10/40—Organic transistors
    • H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
    • H10K10/462—Insulated gate field-effect transistors [IGFETs]
    • H10K10/466—Lateral bottom-gate IGFETs comprising only a single gate
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    • H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
    • H10K10/462—Insulated gate field-effect transistors [IGFETs]
    • H10K10/484—Insulated gate field-effect transistors [IGFETs] characterised by the channel regions
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    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H10K71/13—Deposition of organic active material using liquid deposition, e.g. spin coating using printing techniques, e.g. ink-jet printing or screen printing
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    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H10K71/13—Deposition of organic active material using liquid deposition, e.g. spin coating using printing techniques, e.g. ink-jet printing or screen printing
    • H10K71/135—Deposition of organic active material using liquid deposition, e.g. spin coating using printing techniques, e.g. ink-jet printing or screen printing using ink-jet printing

Definitions

  • the present invention relates to an organic semiconductor element, a manufacturing method thereof, a composition for forming an organic semiconductor film, a compound, and an organic semiconductor film.
  • An organic transistor having an organic semiconductor film is used in a field effect transistor (FET) used in a liquid crystal display or an organic electroluminescence (EL) display, Radio Frequency Identifier (RFID, RF tag), and the like, because lightening of weight, cost reduction and flexibilization can be achieved.
  • FET field effect transistor
  • EL organic electroluminescence
  • RFID Radio Frequency Identifier
  • An object to be achieved by the present invention is to provide an organic semiconductor element and an organic semiconductor film having high mobility and excellent heat resistance, and a manufacturing method thereof.
  • Another object to be achieved by the present invention is to provide a novel compound that is suitable as an organic semiconductor.
  • Still another object to be achieved by the present invention is to provide a composition for forming an organic semiconductor film in which coating film formability is excellent, with which an organic semiconductor element that has high mobility can be obtained, and in which heat resistance is excellent, an organic semiconductor element in which the composition for forming an organic semiconductor film is used, and a manufacturing method thereof.
  • An organic semiconductor element comprising: a compound represented by Formula 1 below in an organic semiconductor layer,
  • X 11 and X 12 each independently represent a chalcogen atom
  • Z 1a to Z 1j each independently represent a hydrogen atom or a halogen atom
  • a 11 represents ⁇ CR A11 — or a nitrogen atom
  • R A11 represents a hydrogen atom or a group represented by R 11
  • a 12 represents ⁇ CR A12 — or a nitrogen atom
  • R A12 represents a hydrogen atom or a group represented by R 12
  • n1 represents 0 or 1
  • p1 represents an integer of 0 to 2 in a case where A 11 is ⁇ CR A11 — and represents 0 or 1 in a case where A 11 is a nitrogen atom
  • q1 represents an integer of 0 to 2 in a case where A 12 is ⁇ CR A12 — and represents 0 or 1 in a case where A 12 is a nitrogen atom
  • R 11 and R 12 each independently represent a halogen atom, an aryl group, a heteroaryl group, or
  • S W represents a single bond or an alkylene group represented by —(CR S 2 ) k —, R S each independently represent a hydrogen atom or a halogen atom, k represents an integer of 1 to 17, L W represents a single bond, a divalent linking group represented by any one of Formulae L-1 to L-16 below, or a group obtained by bonding any two or more of divalent linking groups represented by Formulae L-1 to L-16 below, T W represents an alkyl group, a cyano group, a vinyl group, an ethynyl group, an aryl group, a heteroaryl group, an oxyethylene group, an oligooxyethylene group of which the repetition number of oxyethylene units is two or greater, an oligosiloxane group having two or more silicon atoms, or a trialkylsilyl group,
  • ⁇ 4> The organic semiconductor element according to any one of ⁇ 1> to ⁇ 3>, in which at least one of p1 or q1 is not 0.
  • ⁇ 5> The organic semiconductor element according to any one of ⁇ 1> to ⁇ 4>, in which at least one of p1 or q1 is not 0, and at least one of R 11 or R 12 is a group represented by Formula W.
  • ⁇ 6> The organic semiconductor element according to any one of ⁇ 1> to ⁇ 5>, in which p1 and q1 are 1.
  • ⁇ 7> The organic semiconductor element according to any one of ⁇ 1> to ⁇ 6>, in which both of X 11 and X 12 are S atoms, A 11 is ⁇ CR A11 —, and A 12 is ⁇ CR A12 —.
  • X 21 and X 22 each independently represent a chalcogen atom
  • W 21 and W 22 each independently represent a group represented by Formula W.
  • ⁇ 16> The organic semiconductor element according to any one of ⁇ 1> to ⁇ 15>, in which a group represented by Formula W is an alkyl group.
  • a composition for forming an organic semiconductor film comprising: a solvent having a boiling point of 100° C. or higher; and a compound represented by Formula 1, in which a content of the compound represented by Formula 1 is 20 mass % or less with respect to a total amount of the composition for forming an organic semiconductor film.
  • composition for forming an organic semiconductor film according to any one of ⁇ 17> to ⁇ 21>, in which p1 and q1 is 1.
  • composition for forming an organic semiconductor film according to any one of ⁇ 17> to ⁇ 32>, further comprising: a binder polymer, in which a content of the binder polymer is 10 mass % or less with respect to a total amount of the composition for forming an organic semiconductor film.
  • a method of manufacturing an organic semiconductor film comprising: an applying step of applying the composition for forming an organic semiconductor film according to any one of ⁇ 17> to ⁇ 33> to a substrate, and a removing step of removing at least a portion of the solvent having a boiling point of 100° C. or higher included in the composition for forming an organic semiconductor film.
  • ⁇ 36> The method of manufacturing the organic semiconductor film according to ⁇ 35>, in which the applying step is performed by an ink jet method or a flexographic printing method.
  • a method of manufacturing an organic semiconductor element comprising: an applying step of applying the composition for forming an organic semiconductor film according to any one of ⁇ 17> to ⁇ 33> to a substrate, and a removing step of removing at least a portion of the solvent having a boiling point of 100° C. or higher included in the composition for forming an organic semiconductor film.
  • an organic semiconductor element and an organic semiconductor film having high mobility and excellent heat resistance it is possible to provide an organic semiconductor element and an organic semiconductor film having high mobility and excellent heat resistance, and a manufacturing method thereof.
  • the present invention it is possible to provide a composition for forming an organic semiconductor film in which coating film formability is excellent, with which an organic semiconductor element that has high mobility can be obtained, and in which heat resistance is excellent, an organic semiconductor element in which the composition for forming an organic semiconductor film is used, and a manufacturing method thereof.
  • FIG. 1 is a schematic cross-sectional view of an aspect of an organic semiconductor element of the present invention.
  • FIG. 2 is a schematic cross-sectional view of another aspect of the organic semiconductor element of the present invention.
  • an organic EL element refers to an organic electroluminescence element.
  • an “alkyl group” includes not only an alkyl group not having a substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • the organic semiconductor element according to the present invention includes a compound (hereinafter, referred to as a “specific compound”) represented by Formula 1 above in an organic semiconductor layer.
  • the compound represented by Formula 1 above is preferably an organic semiconductor compound.
  • an organic semiconductor element or an organic semiconductor film containing the compound represented by Formula 1 has high mobility and excellent heat resistance, so as to complete the present invention.
  • X 11 and X 12 each independently represent a chalcogen atom
  • Z 1a to Z 1j each independently represent a hydrogen atom or a halogen atom
  • a 11 represents ⁇ CR A11 — or a nitrogen atom
  • R A11 represents a hydrogen atom or a group represented by R 11
  • a 12 represents ⁇ CR A12 — or a nitrogen atom
  • R A12 represents a hydrogen atom or a group represented by R 12
  • n1 represents 0 or 1
  • p1 represents an integer of 0 to 2 in a case where A 11 is ⁇ CR A11 — and represents 0 or 1 in a case where A 11 is a nitrogen atom
  • q1 represents an integer of 0 to 2 in a case where A 12 is ⁇ CR A12 — and represents 0 or 1 in a case where A 12 is a nitrogen atom
  • R 11 and R 12 each independently represent a halogen atom, an aryl group, a heteroaryl group, or
  • S W represents a single bond or an alkylene group represented by —(CR S 2 ) k —, R S each independently represent a hydrogen atom or a halogen atom, k represents an integer of 1 to 17, L W represents a single bond, a divalent linking group represented by any one of Formulae L-1 to L-16 below, or a group obtained by bonding any two or more of divalent linking groups represented by Formulae L-1 to L-16 below, T W represents an alkyl group, a cyano group, a vinyl group, an ethynyl group, an aryl group, a heteroaryl group, an oxycthylene group, an oligooxycthylene group of which the repetition number of oxyethylene units is two or greater, an oligosiloxane group having two or more silicon atoms, or a trialkylsilyl group.
  • the specific compound according to the present invention is preferably an organic semiconductor compound.
  • the specific compound according to the present invention is a novel compound.
  • the specific compound according to the present invention can be suitably used for an organic semiconductor element, an organic semiconductor film, and a composition for forming an organic semiconductor film.
  • X 11 and X 12 each independently represent a chalcogen atom, it is preferable that X 11 and X 12 each independently represent an O atom or an S atom, and it is more preferable that both of X 11 and X 12 are S atoms.
  • the chalcogen atom refers to an atom in Group 16 including an O atom.
  • Z 1a to Z 1j each independently represent a hydrogen atom or a halogen atom, and it is preferable that all of Z 1a to Z 1j are hydrogen atoms.
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferable.
  • a 11 represents ⁇ CR A11 — or an nitrogen atom, and ⁇ CR A11 — is preferable.
  • R A11 represents a hydrogen atom or a group represented by R 11 , and a hydrogen atom is preferable.
  • the expression “R A11 represents a group represented by R 11 ” refers to a case where one of R 11 's of which the number is specified by p1 in Formula 1 is bonded to a carbon atom in A 11 .
  • a 12 represents ⁇ CR A12 — or a nitrogen atom, and ⁇ CR A12 — is preferable.
  • R A12 represents a hydrogen atom or a group represented by R 12 , and a hydrogen atom is preferable.
  • the expression “R A12 represents a group represented by R 12 ” refers to a case where one of R 12 's of which the number is specified by q1 in Formula 1 is bonded to a carbon atom in A 2 .
  • n1 represents 0 or 1 and preferably 0.
  • p1 represents an integer of 0 to 2, preferably represents 1 or 2, more preferably 1. In a case where A 11 is a nitrogen atom, p1 represents 0 or 1 and preferably represents 1. In a case where A 11 is ⁇ CR A11 —, and p1 is 1, R 11 is preferably bonded to a carbon atom positioned between A 11 and X 11 , not a carbon atom included in A 11 .
  • q1 represents an integer of 0 to 2, preferably represents 1 or 2, and more preferably represents 1. In a case where A 12 is a nitrogen atom, q1 represents 0 or 1 and preferably represents 1. In a case where A 12 is ⁇ CR A12 — and q1 is 1, R 12 is preferably bonded to a carbon atom positioned between A 12 and X 12 , not a carbon atom included in A 12 .
  • R 11 and R 12 each independently represent a halogen atom, an aryl group, a heteroaryl group, or a group represented by Formula W below and preferably represents a group represented by Formula W. —S W -L W -T W (W)
  • S W represents a single bond or an alkylene group represented by —(CR S 2 ) k — and preferably represents a single bond.
  • R S each independently represent a hydrogen atom or a halogen atom and preferably a hydrogen atom.
  • k represents an integer of 1 to 17, preferably represents an integer of 1 to 15, and more preferably an integer of 1 to 10.
  • L W represents a single bond, a divalent linking group represented by any one of Formulae L-1 to L-16, or a group obtained by bonding any two or more of divalent linking groups represented by Formulae L-1 to L-16, preferably represents a single bond, a divalent linking group represented by any one of Formulae L-1 to L-4 and Formulae L-13 to L-16, or a divalent linking group obtained by bonding two or more divalent linking groups represented by any one of Formulae L-1 to L-4 and Formulae L-13 to L-16, more preferably a single bond or a divalent linking group represented by any one of Formulae L-1 to L-4 and Formulae L-13 to L-16, and even more preferably a divalent linking group represented by any one of Formulae L-1, L-3, L-15, and L-16.
  • L W preferably represents a single bond or a divalent linking group represented by any one of Formula L-1 and Formulae L-13 to L-16.
  • T W represented by an alkyl group, a cyano group, a vinyl group, an ethynyl group, an aryl group, a heteroaryl group, an oxyethylene group, an oligooxyethylene group of which the repetition number of oxyethylene units is two or greater, an oligosiloxane group having two or more silicon atoms, or a trialkylsilyl group.
  • the alkyl group is preferably an alkyl group having 2 to 18 carbon atoms, more preferably an alkyl group having 3 to 15 carbon atoms, and even more preferably an alkyl group having 4 to 13 carbon atoms.
  • the alkyl group may have any one of a linear shape, a branched shape, or a cyclic shape, or may have a structure obtained by combining these. However, a linear or branched alkyl group is preferable, and a linear alkyl group is more preferable.
  • the alkyl group may be substituted and preferable examples of the substituent include a halogen atom.
  • aryl group an aromatic hydrocarbon group
  • examples of the aryl group include a group obtained by removing one hydrogen atom from benzene, naphthalene, anthracene, or the like.
  • a group obtained by removing one hydrogen atom from benzene is preferable.
  • the aryl group may be substituted but is preferably not substituted.
  • Examples of a heteroatom included in a heteroaryl group include an oxygen atom, a nitrogen atom, and a sulfur atom.
  • An oxygen atom and a sulfur atom are preferable, and a sulfur atom is more preferable.
  • heteroaryl group examples include a group obtained by removing one hydrogen atom from a thiophene ring, a furan ring, a pyran ring, a pyrrole ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, a selenophene ring, an imidazole ring, and the like.
  • a group obtained by removing one hydrogen atom from a thiophene ring or a furan ring is more preferable, and a group obtained by removing one hydrogen atom from a thiophene ring is even more preferable.
  • the heteroaryl group may be further substituted, but it is preferable that the heteroaryl group is not substituted.
  • the oligooxyethylene group of which the repetition number of oxyethylene units is two or greater is preferably an oligooxyethylene group of which the repetition number is one to five and more preferably an oligooxyethylene group of which the repetition number is one to three.
  • the oligosiloxane group having two or more silicon atoms is preferably an oligosiloxane group having one to five silicon atoms and more preferably an oligosiloxane group having one to three silicon atoms.
  • wavy line portions represent bonding positions to S W
  • * represents a bonding position to T W or a bonding position to a divalent linking group selected from the group consisting of other L-1 to L-16.
  • p13 represents an integer of 0 to 4
  • p14, p15, and p16 each independently represent an integer of 0 to 2
  • R L1 , R L21 , R L22 , R L13 , R L14 , R L15 , and R L16 each independently represent a hydrogen atom or a substituent.
  • the number of linkages of the divalent linking groups represented by any one of Formulae L-1 to L-16 is preferably 2 to 4 and more preferably 2 or 3.
  • R L1 , R L21 , R L22 , R L13 , R L14 , R L15 , and R L16 each independently represent a hydrogen atom or a substituent and preferably represent a hydrogen atom.
  • substituents include various substituents exemplified as T W in Formula 1 above.
  • R L1 's, R L13 's, R L14 's, R L15 's, and R L16 's may be identical to or different from each other.
  • R L1 's, R L21 's, and R L22 's may form ring structures by being bonded to T W adjacent to each other or may form a fused ring as the ring structure.
  • the group represented by Formula W is preferably an alkyl group, more preferably an alkyl group having 2 to 18 carbon atoms, even more preferably an alkyl group having 3 to 15 carbon atoms, and particularly preferably an alkyl group having 4 to 13 carbon atoms.
  • the group represented by Formula W is an alkyl group, it is preferable that S W and L W are single bonds, and T W is an alkyl group.
  • At least one of p1 or q1 is not 0, and it is more preferable that at least one of p1 or q1 is not 0, and at least one of R 11 or R 12 is a group represented by Formula W.
  • both of X 11 and X 12 are S atoms, A 11 is ⁇ CR A11 —, and A 12 is ⁇ CR A12 —, it is more preferable that both of X 11 and X 12 are S atoms, A 11 is ⁇ CR A11 —, A 12 is ⁇ CR A12 —, and both of R A11 and R A12 are hydrogen atoms.
  • the compound represented by Formula 1 is preferably a compound represented by Formula 2 below.
  • X 21 and X 22 each independently represent a chalcogen atom, preferably an O atom or a S atom. It is more preferable that both of X 21 and X 22 are S atoms.
  • W 21 and W 22 each independently represent a group represented by Formula W above, and a preferable aspect thereof is the same as the preferable aspect described in the group represented by Formula W above.
  • the compound represented by Formula 1 above is preferably a line symmetric structure.
  • a compound having a line symmetric structure means that a structural formula thereof is line symmetric with respect to the entire molecule.
  • the compound represented by Formula 1 is preferably a compound represented by Formulae 3 to 5 below.
  • X 11 , X 12 , Z 1a to Z 1j , A 11 , A 12 , p1, q1, R 11 , and R 12 have the same meaning as X 11 , X 12 , Z 1a to Z 1j , A 11 , A 12 , p1, q1, R 11 , and R 12 in Formula 1, and preferable aspects thereof are also the same.
  • X 21 , X 22 , W 21 , and W 22 have the same meaning as X 21 , X 22 , W 21 , and W 22 in Formula 2, and preferable aspects thereof are also the same.
  • X a1 , X a2 , R a11 , R a12 , R a21 , R a22 , X b1 , X b2 , R b11 , R b12 , R b21 , R b22 , X c1 , X c2 , R c11 , and R c21 in Formulae a to c represent structures presented in Tables 1 to 59.
  • Ph represents a phenyl group
  • -Ph- represents a phenylene group
  • * represents a bonding portion to another structure.
  • the content of the specific compound is preferably 30 to 100 mass %, more preferably 50 to 100 mass %, and even more preferably 70 to 100 mass %. In a case where a binder polymer described below is not contained, the content is preferably 90 to 100 mass % and more preferably 95 to 100 mass %.
  • the organic semiconductor layer of the organic semiconductor element according to the present invention preferably contains the binder polymer.
  • the organic semiconductor element according to the present invention may be an organic semiconductor element having a layer including the organic semiconductor layer and the binder polymer.
  • the types of the binder polymer are not particularly limited, and well-known binder polymers can be used.
  • binder polymer examples include a polystyrene resin, an acrylic resin, rubber, and a thermoplastic elastomer.
  • a polymer compound (a polymer having a monomer unit having a benzene ring group) having a benzene ring is preferable.
  • the content of the monomer unit having a benzene ring group is not particularly limited. However, the content is preferably 50 mol % or greater, more preferably 70 mol % or greater, and even more preferably 90 mol % or greater with respect to the entire monomer unit.
  • the upper limit is not particularly limited, but examples of the upper limit include 100 mol %.
  • binder polymer examples include polystyrene, poly( ⁇ -methylstyrene), polyvinyl cinnamate, poly(4-vinylphenyl), and poly(4-methylstyrene).
  • a weight-average molecular weight of the binder polymer is not particularly limited, but is preferably 1,000 to 2,000,000, more preferably 3,000 to 1,000,000, and even more preferably 5,000 to 600,000.
  • the binder polymer exhibits solubility higher than the solubility of the specific compound in a used solvent. If the above aspect is adopted, mobility and heat stability of the obtained organic semiconductor are further improved.
  • a content of the binder polymer in the organic semiconductor layer of the organic semiconductor element of the present invention is preferably 1 to 200 parts by mass, more preferably 10 to 150 parts by mass, and even more preferably 20 to 120 parts by mass with respect to 100 parts by mass of the content of the specific compound. If the content is within the above range, mobility and heat stability of the obtained organic semiconductor are further improved.
  • binder polymer may be included in the organic semiconductor layer according to the organic semiconductor element of the present invention.
  • a content of the components other than the specific compound and the binder polymer is preferably 10 mass % or less, more preferably 5 mass % or less, even more preferably 1 mass % or less, and particularly preferably 0.1 mass % or less. If the content of other components is within the above range, film formability is improved, and mobility and heat stability of the obtained organic semiconductor are further improved.
  • the method of forming the organic semiconductor layer according to the organic semiconductor element of the present invention is not particularly limited.
  • a desired organic semiconductor layer can be formed by applying the composition for forming the organic semiconductor film according to the present invention described below to a source electrode, a drain electrode, and a gate insulating film and performing a drying treatment, if necessary.
  • the organic semiconductor element and an organic semiconductor film of the present invention is preferably manufactured using the composition for forming an organic semiconductor film of the present invention described below.
  • a method of manufacturing an organic semiconductor film or an organic semiconductor element by using the composition for forming an organic semiconductor film of the present invention is not particularly limited, and known methods can be adopted. Examples thereof include a method of manufacturing an organic semiconductor film by applying the composition onto a predetermined base material and if necessary, performing a drying treatment.
  • the method of applying the composition onto a base material is not particularly limited, and known methods can be adopted. Examples thereof include an ink jet printing method, a flexographic printing method, a bar coating method, a spin coating method, a knife coating method, a doctor blade method, and the like. Among these, an ink jet printing method and a flexographic printing method are preferable.
  • Preferred examples of the flexographic printing method include an aspect in which a photosensitive resin plate is used as a flexographic printing plate. By printing the composition onto a substrate according to the aspect, a pattern can be easily formed.
  • the method of manufacturing an organic semiconductor element and an organic semiconductor film according to the present invention preferably include an applying step of applying an composition for forming an organic semiconductor film according to the present invention to a substrate and a removing step of removing at least a portion of a solvent having a boiling point of 100° C. or higher included in the composition for forming the organic semiconductor film.
  • composition for forming the organic semiconductor film according to the present invention contains a solvent having a boiling point of 100° C. or higher (hereinafter, referred to a “specific solvent”).
  • the specific solvent examples include a hydrocarbon-based solvent such as octane, decane, toluene, xylene, mesitylene, ethylbenzene, decalin, 1-methylnaphthalene, tetralin, and dimethyltetralin, a ketone-based solvent such as methyl isobutyl ketone and cyclohexanone, a halogenated hydrocarbon-based solvent such as tetrachloroethane, chlorobenzene, dichlorobenzene, chlorotoluene, 1-fluoronaphthalene, and 1-chloronaphthalene, an ester-based solvent such as butyl acetate and amyl acetate, an alcohol-based solvent such as butanol, pentanol, hexanol, cyclohexanol, methyl cellosolve, ethyl cellosolve, and ethylene glycol, an ether-based solvent
  • the specific solvent may be used singly or two or more types thereof may be used in combination.
  • hydrocarbon-based solvent a hydrocarbon-based solvent, a halogenated hydrocarbon-based solvent and/or an ether-based solvent are preferable, toluene, xylene, mesitylene, tetralin, dichlorobenzene, or anisole is more preferable, and toluene is even more preferable.
  • the specific solvent is the aforementioned solvent, coating properties are excellent, and thus an organic semiconductor film can be easily formed.
  • the boiling point of the specific solvent in normal pressure is 100° C. or higher, preferably 100° C. to 300° C., more preferably 100° C. to 200° C., and even more preferably 100° C. to 150° C.
  • the drying treatment in the removing step is a treatment performed if necessary, and the optimal treatment conditions are suitably selected according to the type of the specific compound used and the solvent.
  • a heating temperature is preferably 30° C. to 100° C. and more preferably 40° C. to 80° C.
  • a heating time is preferably 10 to 300 minutes and more preferably 30 to 180 minutes.
  • a thickness of the formed organic semiconductor layer is not particularly limited. From the viewpoint of mobility and heat stability of the obtained organic semiconductor, the film thickness is preferably 10 to 500 nm and more preferably 30 to 200 nm.
  • the organic semiconductor element is not particularly limited, but is preferably an organic semiconductor element having 2 to 5 terminals, and more preferably an organic semiconductor element having 2 or 3 terminals.
  • the organic semiconductor element is not a photoelectric conversion element.
  • the organic semiconductor element according to the present invention is preferably a non-luminous organic semiconductor element.
  • Examples of a 2-terminal element include a rectifier diode, a constant voltage diode, a PIN diode, a Schottky barrier diode, a surge protection diode, a diac, a varistor, a tunnel diode, and the like.
  • Examples of a 3-terminal element include a bipolar transistor, a Darlington transistor, a field effect transistor, insulated gate bipolar transistor, a uni-junction transistor, a static induction transistor, a gate turn-off thyristor, a triac, a static induction thyristor, and the like.
  • a rectifier diode and transistors are preferable, and a field effect transistor is more preferable.
  • FIG. 1 is a schematic cross-sectional view of an aspect of an organic semiconductor element (organic thin film transistor (organic TFT)) of the present invention.
  • organic semiconductor element organic thin film transistor (organic TFT)
  • an organic thin film transistor 100 includes a substrate 10 , a gate electrode 20 disposed on the substrate 10 , a gate insulating film 30 covering the gate electrode 20 , a source electrode 40 and a drain electrode 42 which contact a surface of the gate insulating film 30 that is on the side opposite to the gate electrode 20 side, an organic semiconductor film 50 covering a surface of the gate insulating film 30 between the source electrode 40 and the drain electrode 42 , and a sealing layer 60 covering each member.
  • the organic thin film transistor 100 is a bottom gate-bottom contact type organic thin film transistor.
  • the organic semiconductor film 50 corresponds to a film formed of the composition described above.
  • the substrate the gate electrode, the gate insulating film, the source electrode, the drain electrode, the organic semiconductor film, the sealing layer, and methods for forming each of these will be specifically described.
  • the substrate plays a role of supporting the gate electrode, the source electrode, the drain electrode, and the like which will be described later.
  • the type of the substrate is not particularly limited, and examples thereof include a plastic substrate, a glass substrate, a ceramic substrate, and the like. Among these, from the viewpoint of applicability to each device and costs, a glass substrate or a plastic substrate is preferable.
  • thermosetting resin for example, an epoxy resin, a phenol resin, a polyimide resin, or a polyester resin (for example, polyethylene terephthalate (PET) or polyethylene naphthalate (PEN)) and a thermoplastic resin (for example, a phenoxy resin, a polyethersulfone, polysulfone, or polyphenylene sulfone).
  • a thermosetting resin for example, an epoxy resin, a phenol resin, a polyimide resin, or a polyester resin (for example, polyethylene terephthalate (PET) or polyethylene naphthalate (PEN)
  • thermoplastic resin for example, a phenoxy resin, a polyethersulfone, polysulfone, or polyphenylene sulfone.
  • Examples of materials of the ceramic substrate include alumina, aluminum nitride, zirconia, silicon, silicon nitride, silicon carbide, and the like.
  • Examples of materials of the glass substrate include soda lime glass, potash glass, borosilicate glass, quartz glass, aluminosilicate glass, lead glass, and the like.
  • Examples of materials of the gate electrode, the source electrode, and the drain electrode include a metal such as gold (Au), silver, aluminum (Al), copper, chromium, nickel, cobalt, titanium, platinum, tantalum, magnesium, calcium, barium, or sodium; a conductive oxide such as InO 2 , SnO 2 , or indium tin oxide (ITO); a conductive polymer such as polyaniline, polypyrrole, polythiophene, polyacetylene, or polydiacetylene; a semiconductor such as silicon, germanium, or gallium arsenide; a carbon material such as fullerene, carbon nanotubes, or graphite; and the like.
  • a metal is preferable, and silver and aluminum are more preferable.
  • a thickness of each of the gate electrode, the source electrode, and the drain electrode is not particularly limited, but is preferably 20 to 200 nm.
  • a method of forming the gate electrode, the source electrode, and the drain electrode is not particularly limited, but examples thereof include a method of vacuum vapor-depositing or sputtering an electrode material onto a substrate, a method of coating a substrate with a composition for forming an electrode, a method of printing a composition for forming an electrode onto a substrate, and the like.
  • examples of the patterning method include a photolithography method; a printing method such as ink jet printing, screen printing, offset printing, or relief printing; a mask vapor deposition method; and the like.
  • Examples of materials of the gate insulating film include a polymer such as polymethyl methacrylate, polystyrene, polyvinylphenol, polyimide, polycarbonate, polyester, polyvinylalcohol, polyvinyl acetate, polyurethane, polysulfone, polybenzoxazole, polysilsesquioxane, an epoxy resin, or a phenol resin; an oxide such as silicon dioxide, aluminum oxide, or titanium oxide; a nitride such as silicon nitride; and the like.
  • a polymer is preferable.
  • a polymer is used as the material of the gate insulating film
  • a cross-linking agent for example, melamine
  • the cross-linking agent is used in combination, the polymer is cross-linked, and durability of the formed gate insulating film is improved.
  • a film thickness of the gate insulating film is not particularly limited, but is preferably 100 to 1,000 nm.
  • a method of forming the gate insulating film is not particularly limited, but examples thereof include a method of coating a substrate, on which the gate electrode is formed, with a composition for forming a gate insulating film, a method of vapor-depositing or sputtering the material of the gate insulating film onto a substrate on which the gate electrode is formed, and the like.
  • a method of coating the aforementioned substrate with the composition for forming a gate insulating film is not particularly limited, and it is possible to use a known method (a bar coating method, a spin coating method, a knife coating method, or a doctor blade method).
  • the composition may be heated (baked) after coating.
  • the organic semiconductor film according to the present invention is a film formed of the composition for forming the organic semiconductor film according to the present invention.
  • the method of forming the organic semiconductor film is not particularly limited.
  • a desired organic semiconductor film can be formed by applying the aforementioned composition to a source electrode, a drain electrode, and a gate insulating film and performing a drying treatment, if desired.
  • the organic semiconductor element of the present invention preferably has a layer of the aforementioned binder polymer between the aforementioned organic semiconductor layer and an insulating film, and more preferably has a layer of the aforementioned binder polymer between the aforementioned organic semiconductor layer and the gate insulating film.
  • a film thickness of the binder polymer layer is not particularly limited, but is preferably 20 to 500 nm.
  • the binder polymer layer should be a layer containing the aforementioned polymer, and is preferably a layer composed of the aforementioned binder polymer.
  • a method of forming the binder polymer layer is not particularly limited, and a known method (a bar coating method, a spin coating method, a knife coating method, a doctor blade method, or an ink jet method) can be used.
  • the binder polymer layer is formed by performing coating by using a composition for forming a binder polymer layer, for the purpose of removing a solvent, causing cross-linking, or the like, the composition may be heated (baked) after coating.
  • the organic semiconductor element of the present invention preferably includes a sealing layer as an outermost layer.
  • a known sealant can be used in the sealing layer.
  • a thickness of the sealing layer is not particularly limited, but is preferably 0.2 to 10 ⁇ m.
  • a method of forming the sealing layer is not particularly limited, but examples thereof include a method of coating a substrate, on which the gate electrode, the gate insulating film, the source electrode, the drain electrode, and the organic semiconductor film are formed, with a composition for forming a sealing layer, and the like.
  • Specific examples of the method of coating the substrate with the composition for forming a sealing layer are the same as the examples of the method of coating the substrate with the composition for forming a gate insulating film.
  • the composition may be heated (baked) after coating.
  • FIG. 2 is a schematic cross-sectional view of another aspect of the organic semiconductor element (organic thin film transistor) of the present invention.
  • an organic thin film transistor 200 includes the substrate 10 , the gate electrode 20 disposed on the substrate 10 , the gate insulating film 30 covering the gate electrode 20 , the organic semiconductor film 50 disposed on the gate insulating film 30 , the source electrode 40 and the drain electrode 42 disposed on the organic semiconductor film 50 , and the sealing layer 60 covering each member.
  • the source electrode 40 and the drain electrode 42 are formed using the aforementioned composition of the present invention.
  • the organic thin film transistor 200 is a top contact type organic thin film transistor.
  • the substrate, the gate electrode, the gate insulating film, the source electrode, the drain electrode, the organic semiconductor film, and the sealing layer are as described above.
  • FIGS. 1 and 2 the aspects of the bottom gate-bottom contact type organic thin film transistor and the bottom gate-top contact type organic thin film transistor were specifically described.
  • the organic semiconductor element of the present invention can also suitably used in a top gate-bottom contact type organic thin film transistor and a top gate-top contact type organic thin film transistor.
  • the organic thin film transistor described above can be suitably used for electronic paper and a display device.
  • the composition for forming the organic semiconductor film according to the present invention contains a solvent having a boiling point of 100° C. or higher and a compound represented by Formula 1, and a content of the compound represented by Formula 1 is 20 mass % or less with respect to a total amount of the composition for forming the organic semiconductor film.
  • composition for forming the organic semiconductor film according to the present invention preferably contains a binder polymer.
  • the specific compound, the binder polymer, and the solvent in the composition for forming the organic semiconductor film according to the present invention are the same as the aforementioned specific compound, the aforementioned binder polymer, and the aforementioned solvent, and preferable aspects are also the same.
  • the content of the specific compound of the composition for forming the organic semiconductor film according to the present invention is 20 mass % or less, preferably 0.001 to 15 mass %, and more preferably 0.01 to 10 mass % with respect to the total amount of the composition for forming the organic semiconductor film.
  • the total content of the specific compounds is preferably in the range described above. If the content of the specific compound is in the range described above, the organic semiconductor element having high mobility and high driving stability can be obtained, storage stability of the composition for forming the organic semiconductor film is also satisfactory.
  • the content of the specific compound is preferably 30 to 100 mass %, more preferably 50 to 100 mass %, and even more preferably 70 to 100 mass % with respect to the total solid content of the composition for forming the organic semiconductor film.
  • the total content is preferably 90 to 100 mass % and more preferably 95 to 100 mass %.
  • the solid content is an amount of the component except for the volatile component such as the solvent.
  • the content of the binder polymer in the composition for forming the organic semiconductor film according to the present invention is preferably greater than 0 mass % and 20 mass % or less, more preferably 0.01 to 15 mass %, and even more preferably 0.25 to 10 mass % with respect to the total amount of the composition for forming the organic semiconductor film. If the content is in the range described above, mobility and heat resistance of the obtained organic semiconductor become more excellent.
  • composition for forming the organic semiconductor film according to the present invention may include other component in addition to the specific compound and the binder polymer.
  • additives As the component, well-known additives may be used.
  • the content of the component in addition to the specific compound and the binder polymer in the composition for forming the organic semiconductor film according to the present invention is preferably 10 mass % or less, more preferably 5 mass % or less, even more preferably 1 mass % or less, and particularly preferably 0.1 mass % or less with respect to the total solid content. If the content is in the range described above, film formability is improved, and mobility and heat stability of the obtained organic semiconductor are further improved.
  • the viscosity of the composition for forming the organic semiconductor film according to the present invention is not particularly limited. However, in view of excellent coating properties, the viscosity is preferably 3 to 100 mPa ⁇ s, more preferably 5 to 50 mPa ⁇ s, and even more preferably 9 to 40 mPa ⁇ s.
  • the viscosity according to the present invention refers to viscosity at 25° C.
  • a measuring method in conformity of JIS Z8803 is preferable.
  • the method of manufacturing the composition for forming the organic semiconductor film according to the present invention is not particularly limited, and well-known methods can be applied.
  • a desired composition can be obtained by adding a specific amount of a specific compound in the solvent and applying an suitable stirring treatment.
  • the binder polymer is used, the specific compound and the binder polymer are simultaneously or sequentially added, so as to suitably manufacture the composition.
  • E-2 to E-10 were also synthesized in the same manner as in E-1, except for changing an organic zinc compound fused with the intermediate M1 to suitable compounds.
  • a compound C-1 was synthesized according to the method described in JP2010-177637A.
  • a compound C-2 was synthesized according to the method disclosed in WO2013/168048A.
  • An organic semiconductor film was formed by casting this composition to a substrate for measuring FET characteristics which was heated to 90° C. under the nitrogen atmosphere, and an organic thin film transistor element for measuring FET characteristics was obtained.
  • the obtained composition was applied to a substrate for measuring FET characteristics by flexographic printing.
  • a flexographic printability test machine F1 manufactured by IGT Testing Systems
  • AFP DSH 1.70% manufactured by Asahi Kasei Corporation
  • a solid image was used as a flexographic resin version.
  • the ink was applied to the substrate for measuring FET characteristics by ink jet printing.
  • DPP2831 manufactured by FUJIFILM Global Graphic Systems Co., Ltd.
  • 10 pL heads were used, so as to form a solid film with a jetting frequency of 2 Hz and a pitch between dots of 20 ⁇ m.
  • drying was performed for one hour at 70° C., so as to form an organic semiconductor film, and the organic TFT element for measuring FET characteristics was obtained.
  • evaluations of mobility, coating film formability, and heat resistance described below with respect to the organic TFT element obtained by ink jet printing were the same as those of the organic TFT element obtained by casting the composition.
  • carrier mobility was evaluated under normal pressure and the nitrogen atmosphere by employing a semiconductor parameter analyzer (manufactured by Agilent, 4156C) to which a semi automatic prober (manufactured by Vector Semiconductor Co., Ltd., AX-2000) was connected.
  • a semiconductor parameter analyzer manufactured by Agilent, 4156C
  • a semi automatic prober manufactured by Vector Semiconductor Co., Ltd., AX-2000
  • a voltage of ⁇ 80 V was applied between source electrodes and drain electrodes of the respective organic thin film transistor elements (FET elements), a gate voltage was changed in the range of 20 V to ⁇ 100 V, an equation below presenting a drain current Id was used, so as to calculate carrier mobility ⁇ .
  • Id ( w/ 2 L ) ⁇ Ci ( Vg ⁇ Vth ) 2
  • L represents a gate length
  • W represents a gate width
  • Ci capacitance of the insulating layer per unit area
  • Vg represents a gate voltage
  • Vth represents a threshold voltage.
  • the numerical value of the carrier mobility is required to be practically 0.01 or greater, preferably 0.1 or greater, and more preferably 0.3 or greater.
  • the compound according to the present invention or the comparative compound (5 mg) and toluene (1 mL) were mixed and heated to 100° C., so as to obtain a non-luminescent organic semiconductor solution.
  • This coating liquid was casted under nitrogen atmosphere to the entire surface of the substrate which was heated to 90° C. and on which channels for 50 elements were formed, so as to form an organic semiconductor thin film, and 50 organic thin film transistor elements for measuring FET characteristics were obtained. Evaluation standards of the coating film formability were set as below, and the evaluation results were presented in Table 60.
  • Carrier mobility maintenance rate after heating was 95% or greater
  • Carrier mobility maintenance rate after heating was 40% or greater and less than 70%
  • Example 1 E-1 1.1 A A A Example 2 E-2 1 B A A Example 3 E-3 0.5 A A A Example 4 E-4 0.7 B A A Example 5 E-5 0.6 A A B Example 6 E-6 0.3 A A A Example 7 E-7 0.05 B A A Example 8 E-8 0.03 B A B Example 9 E-9 0.03 C A A Example 10 E-10 0.01 B A A Comparative C-1 No C B N/A Example 1 Charac- teristics Comparative C-2 5 ⁇ 10 ⁇ 3 C B D Example 2
  • Respective evaluations were performed in the same manner as in Examples 1 to 10 and Comparative Examples 1 to 2 except for mixing the specific compound of the present invention or the comparative compound presented in Table 61, the binder polymer presented in Table 61, and the solvent presented in Table 61 in the concentrations presented in Table 61, performing heating to 100° C., and using the resultant as the composition for forming the organic semiconductor film.
  • the respective evaluation results are presented in Table 61.
  • the organic semiconductor films were formed in the same manner as in Example 1 to 16 except for weighing the specific compounds and toluene (1 mL) presented in Tables 60 and 61 and further the binder polymer (5 mg) in the examples presented in Table 61 such that the content of the respective specific compounds become 21 mass %, performing mixture, performing heating to 100° C., and using the resultant as the composition for forming the organic semiconductor film.
  • the binder polymer 5 mg

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Abstract

An object to be achieved by the present invention is to provide an organic semiconductor element and an organic semiconductor film having high mobility and excellent heat resistance, and a manufacturing method thereof, to provide a novel compound that is suitable as an organic semiconductor, and to provide a composition for forming an organic semiconductor film in which coating film formability is excellent, with which an organic semiconductor element that has high mobility can be obtained, and in which heat resistance is excellent, an organic semiconductor element in which the composition for forming an organic semiconductor film is used, and a manufacturing method thereof.
The organic semiconductor element according to the present invention includes a compound represented by Formula 1 below included in an organic semiconductor layer.
Figure US10497881-20191203-C00001

Description

CROSS-REFERENCE TO RELATED APPLICATION
This application is a continuation application of International Application No. PCT/JP2015/082668, filed Nov. 20, 2015, the disclosure of which is incorporated herein by reference in its entirety. Further, this application claims priority from Japanese Patent Application No. 2014-237888, filed Nov. 25, 2014, the disclosure of which is incorporated herein by reference in its entirety.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to an organic semiconductor element, a manufacturing method thereof, a composition for forming an organic semiconductor film, a compound, and an organic semiconductor film.
2. Description of the Related Art
An organic transistor having an organic semiconductor film (organic semiconductor layer) is used in a field effect transistor (FET) used in a liquid crystal display or an organic electroluminescence (EL) display, Radio Frequency Identifier (RFID, RF tag), and the like, because lightening of weight, cost reduction and flexibilization can be achieved.
As the organic semiconductor in the related art, those disclosed in JP2010-177637A and WO2013/168048A are known.
SUMMARY OF THE INVENTION
An object to be achieved by the present invention is to provide an organic semiconductor element and an organic semiconductor film having high mobility and excellent heat resistance, and a manufacturing method thereof.
Another object to be achieved by the present invention is to provide a novel compound that is suitable as an organic semiconductor.
Still another object to be achieved by the present invention is to provide a composition for forming an organic semiconductor film in which coating film formability is excellent, with which an organic semiconductor element that has high mobility can be obtained, and in which heat resistance is excellent, an organic semiconductor element in which the composition for forming an organic semiconductor film is used, and a manufacturing method thereof.
The objects of the present invention are solved by the means described in <1>, <17>, <34>, <35>, <37>, <38>, and <40> below. <1> to <16>, <18> to <33>, <36>, and <39> which are preferable embodiments are also described below.
<1> An organic semiconductor element comprising: a compound represented by Formula 1 below in an organic semiconductor layer,
Figure US10497881-20191203-C00002
in Formula 1, X11 and X12 each independently represent a chalcogen atom, Z1a to Z1j each independently represent a hydrogen atom or a halogen atom, A11 represents ═CRA11— or a nitrogen atom, RA11 represents a hydrogen atom or a group represented by R11, A12 represents ═CRA12— or a nitrogen atom, RA12 represents a hydrogen atom or a group represented by R12, n1 represents 0 or 1, p1 represents an integer of 0 to 2 in a case where A11 is ═CRA11— and represents 0 or 1 in a case where A11 is a nitrogen atom, q1 represents an integer of 0 to 2 in a case where A12 is ═CRA12— and represents 0 or 1 in a case where A12 is a nitrogen atom, R11 and R12 each independently represent a halogen atom, an aryl group, a heteroaryl group, or a group represented by Formula W below, and
—SW-LW-TW  (W)
in Formula W, SW represents a single bond or an alkylene group represented by —(CRS 2)k—, RS each independently represent a hydrogen atom or a halogen atom, k represents an integer of 1 to 17, LW represents a single bond, a divalent linking group represented by any one of Formulae L-1 to L-16 below, or a group obtained by bonding any two or more of divalent linking groups represented by Formulae L-1 to L-16 below, TW represents an alkyl group, a cyano group, a vinyl group, an ethynyl group, an aryl group, a heteroaryl group, an oxyethylene group, an oligooxyethylene group of which the repetition number of oxyethylene units is two or greater, an oligosiloxane group having two or more silicon atoms, or a trialkylsilyl group,
Figure US10497881-20191203-C00003
Figure US10497881-20191203-C00004
in Formulae L-1 to L-16, * and wavy line portions represent bonding positions to other structures, p13 represents an integer of 0 to 4, p14, p15, and p16 each independently represent an integer of 0 to 2, RL1, RL21, RL22, RL13, RL14, RL15, and RL16 each independently represent a hydrogen atom or a substituent.
<2> The organic semiconductor element according to <1>, in which all of Z1a to Z1j are hydrogen atoms.
<3> The organic semiconductor element according to <1> or <2>, in which n1 is 0.
<4> The organic semiconductor element according to any one of <1> to <3>, in which at least one of p1 or q1 is not 0.
<5> The organic semiconductor element according to any one of <1> to <4>, in which at least one of p1 or q1 is not 0, and at least one of R11 or R12 is a group represented by Formula W.
<6> The organic semiconductor element according to any one of <1> to <5>, in which p1 and q1 are 1.
<7> The organic semiconductor element according to any one of <1> to <6>, in which both of X11 and X12 are S atoms, A11 is ═CRA11—, and A12 is ═CRA12—.
<8> The organic semiconductor element according to any one of <1> to <6>, in which a compound represented by Formula 1 is a compound represented by Formula 2 below,
Figure US10497881-20191203-C00005
in Formula 2, X21 and X22 each independently represent a chalcogen atom, W21 and W22 each independently represent a group represented by Formula W.
<9> The organic semiconductor element according to any one of <1> to <8>, in which the compound represented by Formula 1 is a line symmetric structure.
<10> The organic semiconductor element according to any one of <1> to <9>, in which the number of carbon atoms in the group represented by Formula W is 5 to 40.
<11> The organic semiconductor element according to any one of <1> to <10>, in which LW is a single bond, a divalent linking group represented by any one of Formulae L-1 to L-4 and Formulae L-13 to L-16, or a divalent linking group obtained by bonding two or more divalent linking groups represented by any one of Formulae L-1 to L-4 and Formulae L-13 to L-16.
<12> The organic semiconductor element according to any one of <1> to <11>, in which LW is a single bond or a divalent linking group represented by any one of Formulae L-1 to L-4 and Formulae L-13 to L-16.
<13> The organic semiconductor element according to any one of <1> to <12>, in which SW is a single bond.
<14> The organic semiconductor element according to any one of <1> to <13>, in which LW is a single bond or a divalent linking group represented by any one of Formula L-1 and Formulae L-13 to L-16.
<15> The organic semiconductor element according to any one of <1> to <14>, in which TW is an alkyl group.
<16> The organic semiconductor element according to any one of <1> to <15>, in which a group represented by Formula W is an alkyl group.
<17> A composition for forming an organic semiconductor film, comprising: a solvent having a boiling point of 100° C. or higher; and a compound represented by Formula 1, in which a content of the compound represented by Formula 1 is 20 mass % or less with respect to a total amount of the composition for forming an organic semiconductor film.
<18> The composition for forming an organic semiconductor film according to <17>, in which all of Z1a to Z1j are hydrogen atoms.
<19> The composition for forming an organic semiconductor film according to <17> or <18>, in which n1 is 0.
<20> The composition for forming an organic semiconductor film according to any one of <17> to <19>, in which at least one of p1 or q1 is not 0.
<21> The composition for forming an organic semiconductor film according to any one of <17> to <20>, in which at least one of p1 or q1 is not 0, and at least one of R11 or R12 is a group represented by Formula W.
<22> The composition for forming an organic semiconductor film according to any one of <17> to <21>, in which p1 and q1 is 1.
<23> The composition for forming an organic semiconductor film according to any one of <17> to <22>, in which both of X11 and X12 are S atoms, A11 is ═CRA11—, and A12 is ═CRA12—.
<24> The composition for forming an organic semiconductor film according to any one of <17> to <22>, in which the compound represented by Formula 1 is a compound represented by Formula 2.
<25> The composition for forming an organic semiconductor film according to any one of <17> to <24>, in which the compound represented by Formula 1 is a line symmetric structure.
<26> The composition for forming an organic semiconductor film according to any one of <17> to <25>, in which the number of carbon atoms in the group represented by Formula W is 5 to 40.
<27> The composition for forming an organic semiconductor film according to any one of <17> to <26>, in which LW is a single bond, a divalent linking group represented by any one of Formulae L-1 to L-4 and Formulae L-13 to L-16, and a divalent linking group obtained by bonding two or more divalent linking groups represented by any one of Formulae L-1 to L-4 and Formulae L-13 to L-16.
<28> The composition for forming an organic semiconductor film according to any one of <17> to <27>, in which LW is a single bond or a divalent linking group represented by any one of Formulae L-1 to L-4 and Formulae L-13 to L-16.
<29> The composition for forming an organic semiconductor film according to any one of <17> to <28>, in which SW is a single bond.
<30> The composition for forming an organic semiconductor film according to any one of <17> to <29>, in which LW is a single bond or a divalent linking group represented by any one of Formula L-1 and Formulae L-13 to L-16.
<31> The composition for forming an organic semiconductor film according to any one of <17> to <30>, in which TW is an alkyl group.
<32> The composition for forming an organic semiconductor film according to any one of <17> to <31>, in which a group represented by Formula W is an alkyl group.
<33> The composition for forming an organic semiconductor film according to any one of <17> to <32>, further comprising: a binder polymer, in which a content of the binder polymer is 10 mass % or less with respect to a total amount of the composition for forming an organic semiconductor film.
<34> A compound represented by Formula 1.
<35> A method of manufacturing an organic semiconductor film, comprising: an applying step of applying the composition for forming an organic semiconductor film according to any one of <17> to <33> to a substrate, and a removing step of removing at least a portion of the solvent having a boiling point of 100° C. or higher included in the composition for forming an organic semiconductor film.
<36> The method of manufacturing the organic semiconductor film according to <35>, in which the applying step is performed by an ink jet method or a flexographic printing method.
<37> An organic semiconductor film obtained by the method according to <35> or <36>.
<38> A method of manufacturing an organic semiconductor element, comprising: an applying step of applying the composition for forming an organic semiconductor film according to any one of <17> to <33> to a substrate, and a removing step of removing at least a portion of the solvent having a boiling point of 100° C. or higher included in the composition for forming an organic semiconductor film.
<39> The method of manufacturing the organic semiconductor element according to <38>, in which the applying step is performed by an ink jet method or a flexographic printing method.
<40> An organic semiconductor element manufactured by the method according to <38> or <39>.
According to the present invention, it is possible to provide an organic semiconductor element and an organic semiconductor film having high mobility and excellent heat resistance, and a manufacturing method thereof.
According to the present invention, it is possible to provide a novel compound that is suitable as an organic semiconductor.
According to the present invention, it is possible to provide a composition for forming an organic semiconductor film in which coating film formability is excellent, with which an organic semiconductor element that has high mobility can be obtained, and in which heat resistance is excellent, an organic semiconductor element in which the composition for forming an organic semiconductor film is used, and a manufacturing method thereof.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic cross-sectional view of an aspect of an organic semiconductor element of the present invention.
FIG. 2 is a schematic cross-sectional view of another aspect of the organic semiconductor element of the present invention.
 DESCRIPTION OF THE PREFERRED EMBODIMENTS
Hereinafter, the contents of the present invention will be specifically described. The constituents in the following description will be explained based on typical embodiments of the present invention, but the present invention is not limited to the embodiments. In the specification of the present application, “to” is used to mean that the numerical values listed before and after “to” are a lower limit and an upper limit respectively. Furthermore, in the present invention, an organic EL element refers to an organic electroluminescence element.
In the present specification, in a case where there is no description regarding whether a group (atomic group) is substituted or unsubstituted, the group includes both of a group having a substituent and a group not having a substituent. For example, an “alkyl group” includes not only an alkyl group not having a substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In the present specification, in some cases, a chemical structural formula is described as a simplified structural formula in which a hydrogen atom is omitted.
In the present invention, “mass %” and “weight %” have the same definition, and “part by mass” and “part by weight” have the same definition.
In the present invention, a combination of preferred aspects is more preferable.
(Organic Semiconductor Element and Compound)
The organic semiconductor element according to the present invention includes a compound (hereinafter, referred to as a “specific compound”) represented by Formula 1 above in an organic semiconductor layer.
The compound represented by Formula 1 above is preferably an organic semiconductor compound.
As a result of diligent research, the present inventors found that an organic semiconductor element or an organic semiconductor film containing the compound represented by Formula 1 has high mobility and excellent heat resistance, so as to complete the present invention.
A specific mechanism for exhibiting the effect is not clear, but it is assumed that if the compound represented by Formula 1 has line symmetry with a molecular center as an axis of symmetry in a certain degree or greater, mobility improves since crystallinity becomes excellent, and heat resistance of the organic semiconductor element is improved since a melting point increases.
It is assumed that crystallinity is excellent and mobility is improved, since the compound represented by Formula 1 has a molecular shape that the terminal thiophene ring protrudes from a rod-like structure such as a phenanthrene structure or a picene structure, and the appearance of a liquid crystal layer is suppressed. The mechanism of the suppression of the appearance of the liquid crystal layer as above contributes to the improvement of the heat resistance of the organic semiconductor element.
<Specific Compound>
The specific compound according to the present invention is represented by Formula 1 below.
Figure US10497881-20191203-C00006
In Formula 1, X11 and X12 each independently represent a chalcogen atom, Z1a to Z1j each independently represent a hydrogen atom or a halogen atom, A11 represents ═CRA11— or a nitrogen atom, RA11 represents a hydrogen atom or a group represented by R11, A12 represents ═CRA12— or a nitrogen atom, RA12 represents a hydrogen atom or a group represented by R12, n1 represents 0 or 1, p1 represents an integer of 0 to 2 in a case where A11 is ═CRA11— and represents 0 or 1 in a case where A11 is a nitrogen atom, q1 represents an integer of 0 to 2 in a case where A12 is ═CRA12— and represents 0 or 1 in a case where A12 is a nitrogen atom, R11 and R12 each independently represent a halogen atom, an aryl group, a heteroaryl group, or a group represented by Formula W below.
—SW-LW-TW  (W)
In Formula W, SW represents a single bond or an alkylene group represented by —(CRS 2)k—, RS each independently represent a hydrogen atom or a halogen atom, k represents an integer of 1 to 17, LW represents a single bond, a divalent linking group represented by any one of Formulae L-1 to L-16 below, or a group obtained by bonding any two or more of divalent linking groups represented by Formulae L-1 to L-16 below, TW represents an alkyl group, a cyano group, a vinyl group, an ethynyl group, an aryl group, a heteroaryl group, an oxycthylene group, an oligooxycthylene group of which the repetition number of oxyethylene units is two or greater, an oligosiloxane group having two or more silicon atoms, or a trialkylsilyl group.
Figure US10497881-20191203-C00007
Figure US10497881-20191203-C00008
In Formulae L-1 to L-16, * and wavy line portions represent bonding positions to other structures, p13 represents an integer of 0 to 4, p14, p15, and p16 each independently represent an integer of 0 to 2, RL1, RL21, RL22, RL13, RL14, RL15, and RL16 each independently represent a hydrogen atom or a substituent.
The specific compound according to the present invention is preferably an organic semiconductor compound.
The specific compound according to the present invention is a novel compound.
The specific compound according to the present invention can be suitably used for an organic semiconductor element, an organic semiconductor film, and a composition for forming an organic semiconductor film.
In Formula 1, X11 and X12 each independently represent a chalcogen atom, it is preferable that X11 and X12 each independently represent an O atom or an S atom, and it is more preferable that both of X11 and X12 are S atoms. The chalcogen atom refers to an atom in Group 16 including an O atom.
Z1a to Z1j each independently represent a hydrogen atom or a halogen atom, and it is preferable that all of Z1a to Z1j are hydrogen atoms.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferable.
A11 represents ═CRA11— or an nitrogen atom, and ═CRA11— is preferable.
RA11 represents a hydrogen atom or a group represented by R11, and a hydrogen atom is preferable. The expression “RA11 represents a group represented by R11” refers to a case where one of R11's of which the number is specified by p1 in Formula 1 is bonded to a carbon atom in A11.
A12 represents ═CRA12— or a nitrogen atom, and ═CRA12— is preferable.
RA12 represents a hydrogen atom or a group represented by R12, and a hydrogen atom is preferable. The expression “RA12 represents a group represented by R12” refers to a case where one of R12's of which the number is specified by q1 in Formula 1 is bonded to a carbon atom in A2.
n1 represents 0 or 1 and preferably 0.
In a case where A11 is ═CRA11—, p1 represents an integer of 0 to 2, preferably represents 1 or 2, more preferably 1. In a case where A11 is a nitrogen atom, p1 represents 0 or 1 and preferably represents 1. In a case where A11 is ═CRA11—, and p1 is 1, R11 is preferably bonded to a carbon atom positioned between A11 and X11, not a carbon atom included in A11.
In a case where A12 is ═CRA12—, q1 represents an integer of 0 to 2, preferably represents 1 or 2, and more preferably represents 1. In a case where A12 is a nitrogen atom, q1 represents 0 or 1 and preferably represents 1. In a case where A12 is ═CRA12— and q1 is 1, R12 is preferably bonded to a carbon atom positioned between A12 and X12, not a carbon atom included in A12.
R11 and R12 each independently represent a halogen atom, an aryl group, a heteroaryl group, or a group represented by Formula W below and preferably represents a group represented by Formula W.
—SW-LW-TW  (W)
In Formula W, SW represents a single bond or an alkylene group represented by —(CRS 2)k— and preferably represents a single bond.
RS each independently represent a hydrogen atom or a halogen atom and preferably a hydrogen atom.
k represents an integer of 1 to 17, preferably represents an integer of 1 to 15, and more preferably an integer of 1 to 10.
LW represents a single bond, a divalent linking group represented by any one of Formulae L-1 to L-16, or a group obtained by bonding any two or more of divalent linking groups represented by Formulae L-1 to L-16, preferably represents a single bond, a divalent linking group represented by any one of Formulae L-1 to L-4 and Formulae L-13 to L-16, or a divalent linking group obtained by bonding two or more divalent linking groups represented by any one of Formulae L-1 to L-4 and Formulae L-13 to L-16, more preferably a single bond or a divalent linking group represented by any one of Formulae L-1 to L-4 and Formulae L-13 to L-16, and even more preferably a divalent linking group represented by any one of Formulae L-1, L-3, L-15, and L-16.
LW preferably represents a single bond or a divalent linking group represented by any one of Formula L-1 and Formulae L-13 to L-16.
TW represented by an alkyl group, a cyano group, a vinyl group, an ethynyl group, an aryl group, a heteroaryl group, an oxyethylene group, an oligooxyethylene group of which the repetition number of oxyethylene units is two or greater, an oligosiloxane group having two or more silicon atoms, or a trialkylsilyl group.
The alkyl group is preferably an alkyl group having 2 to 18 carbon atoms, more preferably an alkyl group having 3 to 15 carbon atoms, and even more preferably an alkyl group having 4 to 13 carbon atoms. The alkyl group may have any one of a linear shape, a branched shape, or a cyclic shape, or may have a structure obtained by combining these. However, a linear or branched alkyl group is preferable, and a linear alkyl group is more preferable.
The alkyl group may be substituted and preferable examples of the substituent include a halogen atom.
Examples of the aryl group (an aromatic hydrocarbon group) include a group obtained by removing one hydrogen atom from benzene, naphthalene, anthracene, or the like. A group obtained by removing one hydrogen atom from benzene is preferable.
The aryl group may be substituted but is preferably not substituted.
Examples of a heteroatom included in a heteroaryl group (an aromatic heterocyclic group) include an oxygen atom, a nitrogen atom, and a sulfur atom. An oxygen atom and a sulfur atom are preferable, and a sulfur atom is more preferable.
Examples of the heteroaryl group include a group obtained by removing one hydrogen atom from a thiophene ring, a furan ring, a pyran ring, a pyrrole ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, a selenophene ring, an imidazole ring, and the like. A group obtained by removing one hydrogen atom from a thiophene ring or a furan ring is more preferable, and a group obtained by removing one hydrogen atom from a thiophene ring is even more preferable.
The heteroaryl group may be further substituted, but it is preferable that the heteroaryl group is not substituted.
The oligooxyethylene group of which the repetition number of oxyethylene units is two or greater is preferably an oligooxyethylene group of which the repetition number is one to five and more preferably an oligooxyethylene group of which the repetition number is one to three.
The oligosiloxane group having two or more silicon atoms is preferably an oligosiloxane group having one to five silicon atoms and more preferably an oligosiloxane group having one to three silicon atoms.
In Formulae L-1 to L-16, it is preferable that wavy line portions represent bonding positions to SW, * represents a bonding position to TW or a bonding position to a divalent linking group selected from the group consisting of other L-1 to L-16.
p13 represents an integer of 0 to 4, p14, p15, and p16 each independently represent an integer of 0 to 2, and RL1, RL21, RL22, RL13, RL14, RL15, and RL16 each independently represent a hydrogen atom or a substituent.
In a case where LW represents a linking group obtained by bonding a divalent linking group represented by any one of Formulae L-1 to L-16 above, the number of linkages of the divalent linking groups represented by any one of Formulae L-1 to L-16 is preferably 2 to 4 and more preferably 2 or 3.
RL1, RL21, RL22, RL13, RL14, RL15, and RL16 each independently represent a hydrogen atom or a substituent and preferably represent a hydrogen atom. Examples of the substituent include various substituents exemplified as TW in Formula 1 above.
A plurality of RL1's, RL13's, RL14's, RL15's, and RL16's may be identical to or different from each other. RL1's, RL21's, and RL22's may form ring structures by being bonded to TW adjacent to each other or may form a fused ring as the ring structure.
The group represented by Formula W is preferably an alkyl group, more preferably an alkyl group having 2 to 18 carbon atoms, even more preferably an alkyl group having 3 to 15 carbon atoms, and particularly preferably an alkyl group having 4 to 13 carbon atoms. In a case where the group represented by Formula W is an alkyl group, it is preferable that SW and LW are single bonds, and TW is an alkyl group.
In Formula 1, it is preferable that at least one of p1 or q1 is not 0, and it is more preferable that at least one of p1 or q1 is not 0, and at least one of R11 or R12 is a group represented by Formula W.
In Formula 1, it is preferable that p1 and q1 are 1, it is more preferable that p1 and q1 are 1, and at least one of R11 or R12 is a group represented by Formula W, and it is even more preferable that p1 and q1 are 1, and both of R11 and R12 are groups represented by Formula W.
In Formula 1, it is preferable that both of X11 and X12 are S atoms, A11 is ═CRA11—, and A12 is ═CRA12—, it is more preferable that both of X11 and X12 are S atoms, A11 is ═CRA11—, A12 is ═CRA12—, and both of RA11 and RA12 are hydrogen atoms.
The compound represented by Formula 1 is preferably a compound represented by Formula 2 below.
Figure US10497881-20191203-C00009
In Formula 2, X21 and X22 each independently represent a chalcogen atom, preferably an O atom or a S atom. It is more preferable that both of X21 and X22 are S atoms. W21 and W22 each independently represent a group represented by Formula W above, and a preferable aspect thereof is the same as the preferable aspect described in the group represented by Formula W above.
The compound represented by Formula 1 above is preferably a line symmetric structure.
The expression “a compound has a line symmetric structure” means that a structural formula thereof is line symmetric with respect to the entire molecule. Specifically, the compound represented by Formula 1 is preferably a compound represented by Formulae 3 to 5 below.
It is considered that, if the compound represented by Formula 1 has a line symmetric structure, crystallinity and melting point become high, and mobility or heat resistance of an obtained organic semiconductor element or an obtained organic semiconductor film increase.
Figure US10497881-20191203-C00010
In Formula 3 or 4, X11, X12, Z1a to Z1j, A11, A12, p1, q1, R11, and R12 have the same meaning as X11, X12, Z1a to Z1j, A11, A12, p1, q1, R11, and R12 in Formula 1, and preferable aspects thereof are also the same.
In Formula 5, X21, X22, W21, and W22 have the same meaning as X21, X22, W21, and W22 in Formula 2, and preferable aspects thereof are also the same.
All of the compounds represented by Formulae 3 to 5 have line symmetry having broken lines as symmetry axes.
As specific examples of the specific compound used in the present invention, Compounds 1 to 1475 represented by Formulae a to c below and presented in Tables 1 to 59 are preferably exemplified. However, the present invention is not limited thereto.
Figure US10497881-20191203-C00011
In Compounds 1 to 1475, Xa1, Xa2, Ra11, Ra12, Ra21, Ra22, Xb1, Xb2, Rb11, Rb12, Rb21, Rb22, Xc1, Xc2, Rc11, and Rc21 in Formulae a to c represent structures presented in Tables 1 to 59. In Tables 1 to 59, Ph represents a phenyl group, -Ph- represents a phenylene group, and * represents a bonding portion to another structure.
TABLE 1
Xa1 Xa2 Ra11 Ra12 Ra21 Ra22
Compound 1 S S C4H9—* H C4H9—* H
Compound 2 S S C5H11—* H C5H11—* H
Compound 3 S S C6H13—* H C6H13—* H
Compound 4 S S C7H15—* H C7H15—* H
Compound 5 S S C8H17—* H C8H17—* H
Compound 6 S S C9H19—* H C9H19—* H
Compound 7 S S C10H21—* H C10H21—* H
Compound 8 S S C11H23—* H C11H23—* H
Compound 9 S S C12H25—* H C12H25—* H
Compound 10 S S C13H27—* H C13H27—* H
Compound 11 S S C14H29—* H C14H29—* H
Compound 12 S S C15H31—* H C15H31—* H
Compound 13 S S C16H33—* H C16H33—* H
Compound 14 S S C17H35—* H C17H35—* H
Compound 15 S S C18H37—* H C18H37—* H
Compound 16 S S C5H11—* C5H11—* C5H11—* C5H11—*
Compound 17 S S C6H13—* C6H13—* C6H13—* C6H13—*
Compound 18 S S C7H15—* C7H15—* C7H15—* C7H15—*
Compound 19 S S C8H17—* C8H17—* C8H17—* C8H17—*
Compound 20 S S C9H19—* C9H19—* C9H19—* C9H19—*
Compound 21 S S C10H21—* C10H21—* C10H21—* C10H21—*
Compound 22 S S C11H23—* C11H23—* C11H23—* C11H23—*
Compound 23 S S C12H25—* C12H25—* C12H25—* C12H25—*
Compound 24 S S C13H27—* C13H27—* C13H27—* C13H27—*
Compound 25 S S C14H29—* C14H29—* C14H29—* C14H29—*
Compound 26 S S C15H31—* C15H31—* C15H31—* C15H31—*
Compound 27 S S C16H33—* C16H33—* C16H33—* C16H33—*
Compound 28 S S C17H35—* C17H35—* C17H35—* C17H35—*
Compound 29 S S C18H37—* C18H37—* C18H37—* C18H37—*
Compound 30 S S p-C5H11—Ph—* H p-C5H11—Ph—* H
Compound 31 S S p-C6H13—Ph—* H p-C6H13—Ph—* H
Compound 32 S S p-C7H15—Ph—* H p-C7H15—Ph—* H
Compound 33 S S p-C8H17—Ph—* H p-C8H17—Ph—* H
Compound 34 S S p-C9H19—Ph—* H p-C9H19—Ph—* H
Compound 35 S S p-C10H21—Ph—* H p-C10H21—Ph—* H
Compound 36 S S p-C11H23—Ph—* H p-C11H23—Ph—* H
Compound 37 S S p-C12H25—Ph—* H p-C12H25—Ph—* H
Compound 38 S S p-C13H27—Ph—* H p-C13H27—Ph—* H
Compound 39 S S p-C14H29—Ph—* H p-C14H29—Ph—* H
Compound 40 S S p-C15H31—Ph—* H p-C15H31—Ph—* H
Compound 41 S S p-C16H33—Ph—* H p-C16H33—Ph—* H
Compound 42 S S p-C17H35—Ph—* H p-C17H35—Ph—* H
Compound 43 S S p-C18H37—Ph—* H p-C18H37—Ph—* H
Compound 44 S S p-C5H11—Ph—* p-C5H11—Ph—* p-C5H11—Ph—* p-C5H11—Ph—*
Compound 45 S S p-C6H13—Ph—* p-C6H13—Ph—* p-C6H13—Ph—* p-C6H13—Ph—*
Compound 46 S S p-C7H15—Ph—* p-C7H15—Ph—* p-C7H15—Ph—* p-C7H15—Ph—*
Compound 47 S S p-C8H17—Ph—* p-C8H17—Ph—* p-C8H17—Ph—* p-C8H17—Ph—*
Compound 48 S S p-C9H19—Ph—* p-C9H19—Ph—* p-C9H19—Ph—* p-C9H19—Ph—*
Compound 49 S S p-C10H21—Ph—* p-C10H21—Ph—* p-C10H21—Ph—* p-C10H21—Ph—*
Compound 50 S S p-C11H23—Ph—* p-C11H23—Ph—* p-C11H23—Ph—* p-C11H23—Ph—*
Compound 51 S S p-C12H25—Ph—* p-C12H25—Ph—* p-C12H25—Ph—* p-C12H25—Ph—*
TABLE 2
Xa1 Xa2 Ra11 Ra12 Ra21 Ra22
Compound 52 S S p-C13H27—Ph—* p-C13H27—Ph—* p-C13H27—Ph—* p-C13H27—Ph—*
Compound 53 S S p-C14H29—Ph—* p-C14H29—Ph—* p-C14H29—Ph—* p-C14H29—Ph—*
Compound 54 S S p-C15H31—Ph—* p-C15H31—Ph—* p-C15H31—Ph—* p-C15H31—Ph—*
Compound 55 S S p-C16H33—Ph—* p-C16H33—Ph—* p-C16H33—Ph—* p-C16H33—Ph—*
Compound 56 S S p-C17H35—Ph—* p-C17H35—Ph—* p-C17H35—Ph—* p-C17H35—Ph—*
Compound 57 S S p-C18H37—Ph—* p-C18H37—Ph—* p-C18H37—Ph—* p-C18H37—Ph—*
Compound 58 S S
Figure US10497881-20191203-C00012
 		H
Figure US10497881-20191203-C00013
 		H
Compound 59 S S
Figure US10497881-20191203-C00014
 		H
Figure US10497881-20191203-C00015
 		H
Compound 60 S S
Figure US10497881-20191203-C00016
 		H
Figure US10497881-20191203-C00017
 		H
Compound 61 S S
Figure US10497881-20191203-C00018
 		H
Figure US10497881-20191203-C00019
 		H
Compound 62 S S
Figure US10497881-20191203-C00020
 		H
Figure US10497881-20191203-C00021
 		H
Compound 63 S S
Figure US10497881-20191203-C00022
 		H
Figure US10497881-20191203-C00023
 		H
Compound 64 S S
Figure US10497881-20191203-C00024
 		H
Figure US10497881-20191203-C00025
 		H
Compound 65 S S
Figure US10497881-20191203-C00026
 		H
Figure US10497881-20191203-C00027
 		H
Compound 66 S S
Figure US10497881-20191203-C00028
 		H
Figure US10497881-20191203-C00029
 		H
Compound 67 S S
Figure US10497881-20191203-C00030
 		H
Figure US10497881-20191203-C00031
 		H
Compound 68 S S
Figure US10497881-20191203-C00032
 		H
Figure US10497881-20191203-C00033
 		H
Compound 69 S S
Figure US10497881-20191203-C00034
 		H
Figure US10497881-20191203-C00035
 		H
Compound 70 S S
Figure US10497881-20191203-C00036
 		H
Figure US10497881-20191203-C00037
 		H
Compound 71 S S
Figure US10497881-20191203-C00038
 		H
Figure US10497881-20191203-C00039
 		H
Compound 72 S S
Figure US10497881-20191203-C00040
 		H
Figure US10497881-20191203-C00041
 		H
Compound 73 S S
Figure US10497881-20191203-C00042
 		H
Figure US10497881-20191203-C00043
 		H
TABLE 3
Xa1 Xa2 Ra11 Ra12 Ra21 Ra22
Compound 74 S S
Figure US10497881-20191203-C00044
 		H
Figure US10497881-20191203-C00045
 		H
Compound 75 S S
Figure US10497881-20191203-C00046
 		H
Figure US10497881-20191203-C00047
 		H
Compound 76 S S
Figure US10497881-20191203-C00048
 		H
Figure US10497881-20191203-C00049
 		H
Compound 77 S S
Figure US10497881-20191203-C00050
 		H
Figure US10497881-20191203-C00051
 		H
Compound 78 S S
Figure US10497881-20191203-C00052
 		H
Figure US10497881-20191203-C00053
 		H
Compound 79 S S
Figure US10497881-20191203-C00054
 		H
Figure US10497881-20191203-C00055
 		H
Compound 80 S S
Figure US10497881-20191203-C00056
 		H
Figure US10497881-20191203-C00057
 		H
Compound 81 S S
Figure US10497881-20191203-C00058
 		H
Figure US10497881-20191203-C00059
 		H
Compound 82 S S
Figure US10497881-20191203-C00060
 		H
Figure US10497881-20191203-C00061
 		H
Compound 83 S S
Figure US10497881-20191203-C00062
 		H
Figure US10497881-20191203-C00063
 		H
Compound 84 S S
Figure US10497881-20191203-C00064
 		H
Figure US10497881-20191203-C00065
 		H
Compound 85 S S
Figure US10497881-20191203-C00066
 		H
Figure US10497881-20191203-C00067
 		H
Compound 86 S S
Figure US10497881-20191203-C00068
Figure US10497881-20191203-C00069
Figure US10497881-20191203-C00070
Figure US10497881-20191203-C00071
Compound 87 S S
Figure US10497881-20191203-C00072
Figure US10497881-20191203-C00073
Figure US10497881-20191203-C00074
Figure US10497881-20191203-C00075
Compound 88 S S
Figure US10497881-20191203-C00076
Figure US10497881-20191203-C00077
Figure US10497881-20191203-C00078
Figure US10497881-20191203-C00079
Compound 89 S S
Figure US10497881-20191203-C00080
Figure US10497881-20191203-C00081
Figure US10497881-20191203-C00082
Figure US10497881-20191203-C00083
Compound 90 S S
Figure US10497881-20191203-C00084
Figure US10497881-20191203-C00085
Figure US10497881-20191203-C00086
Figure US10497881-20191203-C00087
Compound 91 S S
Figure US10497881-20191203-C00088
Figure US10497881-20191203-C00089
Figure US10497881-20191203-C00090
Figure US10497881-20191203-C00091
TABLE 4
Xa1 Xa2 Ra11 Ra12 Ra21 Ra22
Compound 92  S S
Figure US10497881-20191203-C00092
Figure US10497881-20191203-C00093
Figure US10497881-20191203-C00094
Figure US10497881-20191203-C00095
Compound 93  S S
Figure US10497881-20191203-C00096
Figure US10497881-20191203-C00097
Figure US10497881-20191203-C00098
Figure US10497881-20191203-C00099
Compound 94  S S
Figure US10497881-20191203-C00100
Figure US10497881-20191203-C00101
Figure US10497881-20191203-C00102
Figure US10497881-20191203-C00103
Compound 95  S S
Figure US10497881-20191203-C00104
Figure US10497881-20191203-C00105
Figure US10497881-20191203-C00106
Figure US10497881-20191203-C00107
Compound 96  S S
Figure US10497881-20191203-C00108
Figure US10497881-20191203-C00109
Figure US10497881-20191203-C00110
Figure US10497881-20191203-C00111
Compound 97  S S
Figure US10497881-20191203-C00112
Figure US10497881-20191203-C00113
Figure US10497881-20191203-C00114
Figure US10497881-20191203-C00115
Compound 98  S S
Figure US10497881-20191203-C00116
Figure US10497881-20191203-C00117
Figure US10497881-20191203-C00118
Figure US10497881-20191203-C00119
Compound 99  S S
Figure US10497881-20191203-C00120
Figure US10497881-20191203-C00121
Figure US10497881-20191203-C00122
Figure US10497881-20191203-C00123
Compound 100 S S
Figure US10497881-20191203-C00124
 		H
Figure US10497881-20191203-C00125
 		H
Compound 101 S S
Figure US10497881-20191203-C00126
 		H
Figure US10497881-20191203-C00127
 		H
Compound 102 S S
Figure US10497881-20191203-C00128
 		H
Figure US10497881-20191203-C00129
 		H
Compound 103 S S
Figure US10497881-20191203-C00130
 		H
Figure US10497881-20191203-C00131
 		H
Compound 104 S S
Figure US10497881-20191203-C00132
 		H
Figure US10497881-20191203-C00133
 		H
Compound 105 S S
Figure US10497881-20191203-C00134
 		H
Figure US10497881-20191203-C00135
 		H
Compound 106 S S
Figure US10497881-20191203-C00136
 		H
Figure US10497881-20191203-C00137
 		H
Compound 107 S S
Figure US10497881-20191203-C00138
 		H
Figure US10497881-20191203-C00139
 		H
Compound 108 S S
Figure US10497881-20191203-C00140
 		H
Figure US10497881-20191203-C00141
 		H
Compound 109 S S
Figure US10497881-20191203-C00142
 		H
Figure US10497881-20191203-C00143
 		H
TABLE 5
Xa1 Xa2 Ra11 Ra12 Ra21 Ra22
Compound 110 S S
Figure US10497881-20191203-C00144
 		H
Figure US10497881-20191203-C00145
 		H
Compound 111 S S
Figure US10497881-20191203-C00146
 		H
Figure US10497881-20191203-C00147
 		H
Compound 112 S S
Figure US10497881-20191203-C00148
 		H
Figure US10497881-20191203-C00149
 		H
Compound 113 S S
Figure US10497881-20191203-C00150
 		H
Figure US10497881-20191203-C00151
 		H
Compound 114 S S
Figure US10497881-20191203-C00152
Figure US10497881-20191203-C00153
Figure US10497881-20191203-C00154
Figure US10497881-20191203-C00155
Compound 115 S S
Figure US10497881-20191203-C00156
Figure US10497881-20191203-C00157
Figure US10497881-20191203-C00158
Figure US10497881-20191203-C00159
Compound 116 S S
Figure US10497881-20191203-C00160
Figure US10497881-20191203-C00161
Figure US10497881-20191203-C00162
Figure US10497881-20191203-C00163
Compound 117 S S
Figure US10497881-20191203-C00164
Figure US10497881-20191203-C00165
Figure US10497881-20191203-C00166
Figure US10497881-20191203-C00167
Compound 118 S S
Figure US10497881-20191203-C00168
Figure US10497881-20191203-C00169
Figure US10497881-20191203-C00170
Figure US10497881-20191203-C00171
Compound 119 S S
Figure US10497881-20191203-C00172
Figure US10497881-20191203-C00173
Figure US10497881-20191203-C00174
Figure US10497881-20191203-C00175
Compound 120 S S
Figure US10497881-20191203-C00176
Figure US10497881-20191203-C00177
Figure US10497881-20191203-C00178
Figure US10497881-20191203-C00179
Compound 121 S S
Figure US10497881-20191203-C00180
Figure US10497881-20191203-C00181
Figure US10497881-20191203-C00182
Figure US10497881-20191203-C00183
Compound 122 S S
Figure US10497881-20191203-C00184
Figure US10497881-20191203-C00185
Figure US10497881-20191203-C00186
Figure US10497881-20191203-C00187
Compound 123 S S
Figure US10497881-20191203-C00188
Figure US10497881-20191203-C00189
Figure US10497881-20191203-C00190
Figure US10497881-20191203-C00191
Compound 124 S S
Figure US10497881-20191203-C00192
Figure US10497881-20191203-C00193
Figure US10497881-20191203-C00194
Figure US10497881-20191203-C00195
Compound 125 S S
Figure US10497881-20191203-C00196
Figure US10497881-20191203-C00197
Figure US10497881-20191203-C00198
Figure US10497881-20191203-C00199
Compound 126 S S
Figure US10497881-20191203-C00200
Figure US10497881-20191203-C00201
Figure US10497881-20191203-C00202
Figure US10497881-20191203-C00203
Compound 127 S S
Figure US10497881-20191203-C00204
Figure US10497881-20191203-C00205
Figure US10497881-20191203-C00206
Figure US10497881-20191203-C00207
TABLE 6
Xa1 Xa2 Ra11 Ra12 Ra21 Ra22
Compound 128 S S H C5H11—* H C5H11—*
Compound 129 S S H C6H13—* H C6H13—*
Compound 130 S S H C7H15—* H C7H15—*
Compound 131 S S H C8H17—* H C8H17—*
Compound 132 S S H C9H19—* H C9H19—*
Compound 133 S S H C10H21—* H C10H21—*
Compound 134 S S H C11H23—* H C11H23—*
Compound 135 S S H C12H25—* H C12H25—*
Compound 136 S S H C13H27—* H C13H27—*
Compound 137 S S H C14H29—* H C14H29—*
Compound 138 S S H C15H31—* H C15H31—*
Compound 139 S S H C16H33—* H C16H33—*
Compound 140 S S H C17H35—* H C17H35—*
Compound 141 S S H C18H37—* H C18H37—*
Compound 142 S S H p-C5H11—Ph—* H p-C5H11—Ph—*
Compound 143 S S H p-C6H13—Ph—* H p-C6H13—Ph—*
Compound 144 S S H p-C7H15—Ph—* H p-C7H15—Ph—*
Compound 145 S S H p-C8H17—Ph—* H p-C8H17—Ph—*
Compound 146 S S H p-C9H19—Ph—* H p-C9H19—Ph—*
Compound 147 S S H p-C10H21—Ph—* H p-C10H21—Ph—*
Compound 148 S S H p-C11H23—Ph—* H p-C11H23—Ph—*
Compound 149 S S H p-C12H25—Ph—* H p-C12H25—Ph—*
Compound 150 S S H p-C13H27—Ph—* H p-C13H27—Ph—*
Compound 151 S S H p-C14H29—Ph—* H p-C14H29—Ph—*
Compound 152 S S H p-C15H31—Ph—* H p-C15H31—Ph—*
Compound 153 S S H p-C16H33—Ph—* H p-C16H33—Ph—*
Compound 154 S S H p-C17H35—Ph—* H p-C17H35—Ph—*
Compound 155 S S H p-C18H37—Ph—* H p-C18H37—Ph—*
Compound 156 S S H
Figure US10497881-20191203-C00208
 		H
Figure US10497881-20191203-C00209
Compound 157 S S H
Figure US10497881-20191203-C00210
 		H
Figure US10497881-20191203-C00211
Compound 158 S S H
Figure US10497881-20191203-C00212
 		H
Figure US10497881-20191203-C00213
Compound 159 S S H
Figure US10497881-20191203-C00214
 		H
Figure US10497881-20191203-C00215
Compound 160 S S H
Figure US10497881-20191203-C00216
 		H
Figure US10497881-20191203-C00217
Compound 161 S S H
Figure US10497881-20191203-C00218
 		H
Figure US10497881-20191203-C00219
Compound 162 S S H
Figure US10497881-20191203-C00220
 		H
Figure US10497881-20191203-C00221
Compound 163 S S H
Figure US10497881-20191203-C00222
 		H
Figure US10497881-20191203-C00223
TABLE 7
Xa1 Xa2 Ra11 Ra12 Ra21 Ra22
Compound 164 S S H
Figure US10497881-20191203-C00224
 		H
Figure US10497881-20191203-C00225
Compound 165 S S H
Figure US10497881-20191203-C00226
 		H
Figure US10497881-20191203-C00227
Compound 166 S S H
Figure US10497881-20191203-C00228
 		H
Figure US10497881-20191203-C00229
Compound 167 S S H
Figure US10497881-20191203-C00230
 		H
Figure US10497881-20191203-C00231
Compound 168 S S H
Figure US10497881-20191203-C00232
 		H
Figure US10497881-20191203-C00233
Compound 169 S S H
Figure US10497881-20191203-C00234
 		H
Figure US10497881-20191203-C00235
Compound 170 S S H H C5H11—* H
Compound 171 S S H H C6H13—* H
Compound 172 S S H H C7H15—* H
Compound 173 S S H H C8H17—* H
Compound 174 S S H H C9H19—* H
Compound 175 S S H H C10H21—* H
Compound 176 S S H H C11H23—* H
Compound 177 S S H H C12H25—* H
Compound 178 S S H H C13H27—* H
Compound 179 S S H H C14H29—* H
Compound 180 S S H H C15H31—* H
Compound 181 S S H H C16H33—* H
Compound 182 S S H H C17H35—* H
Compound 183 S S H H C18H37—* H
Compound 184 S S Ph H C5H11—* H
Compound 185 S S Ph H C6H13—* H
Compound 186 S S Ph H C7H15—* H
Compound 187 S S Ph H C8H17—* H
Compound 188 S S Ph H C9H19—* H
Compound 189 S S Ph H C10H21—* H
Compound 190 S S Ph H C11H23—* H
Compound 191 S S Ph H C12H25—* H
Compound 192 S S Ph H C13H27—* H
Compound 193 S S Ph H C14H29—* H
Compound 194 S S Ph H C15H31—* H
Compound 195 S S Ph H C16H33—* H
Compound 196 S S Ph H C17H35—* H
Compound 197 S S Ph H C18H37—* H
Compound 198 S S
Figure US10497881-20191203-C00236
 		H C5H11—* H
Compound 199 S S
Figure US10497881-20191203-C00237
 		H C6H13—* H
TABLE 8
Xa1 Xa2 Ra11 Ra12 Ra21 Ra22
Compound 200 S S
Figure US10497881-20191203-C00238
 		H C7H15—* H
Compound 201 S S
Figure US10497881-20191203-C00239
 		H C8H17—* H
Compound 202 S S
Figure US10497881-20191203-C00240
 		H C9H19—* H
Compound 203 S S
Figure US10497881-20191203-C00241
 		H C10H21—* H
Compound 204 S S
Figure US10497881-20191203-C00242
 		H C11H23—* H
Compound 205 S S
Figure US10497881-20191203-C00243
 		H C12H25—* H
Compound 206 S S
Figure US10497881-20191203-C00244
 		H C13H27—* H
Compound 207 S S
Figure US10497881-20191203-C00245
 		H C14H29—* H
Compound 208 S S
Figure US10497881-20191203-C00246
 		H C15H31—* H
Compound 209 S S
Figure US10497881-20191203-C00247
 		H C16H33—* H
Compound 210 S S
Figure US10497881-20191203-C00248
 		H C17H35—* H
Compound 211 S S
Figure US10497881-20191203-C00249
 		H C18H37—* H
Compound 212 S S H H H C5H11—*
Compound 213 S S H H H C6H13—*
Compound 214 S S H H H C7H15—*
Compound 215 S S H H H C8H17—*
Compound 216 S S H H H C9H19—*
Compound 217 S S H H H C10H21—*
Compound 218 S S H H H C11H23—*
Compound 219 S S H H H C12H25—*
Compound 220 S S H H H C13H27—*
Compound 221 S S H H H C14H29—*
Compound 222 S S H H H C15H31—*
Compound 223 S S H H H C16H33—*
Compound 224 S S H H H C17H35—*
Compound 225 S S H H H C18H37—*
Compound 226 S S H H p-C5H11—Ph—* H
Compound 227 S S H H p-C6H13—Ph—* H
Compound 228 S S H H p-C7H15—Ph—* H
Compound 229 S S H H p-C8H17—Ph—* H
Compound 230 S S H H p-C9H19—Ph—* H
TABLE 9
Xa1 Xa2 Ra11 Ra12 Ra21 Ra22
Compound 231 S S H H p-C10H21—Ph—* H
Compound 232 S S H H p-C11H23—Ph—* H
Compound 233 S S H H p-C12H25—Ph—* H
Compound 234 S S H H p-C13H27—Ph—* H
Compound 235 S S H H p-C14H29—Ph—* H
Compound 236 S S H H p-C15H31—Ph—* H
Compound 237 S S H H p-C16H33—Ph—* H
Compound 238 S S H H p-C17H35—Ph—* H
Compound 239 S S H H p-C18H37—Ph—* H
Compound 240 S S Ph H p-C5H11—Ph—* H
Compound 241 S S Ph H p-C6H13—Ph—* H
Compound 242 S S Ph H p-C7H15—Ph—* H
Compound 243 S S Ph H p-C8H17—Ph—* H
Compound 244 S S Ph H p-C9H19—Ph—* H
Compound 245 S S Ph H p-C10H21—Ph—* H
Compound 246 S S Ph H p-C11H23—Ph—* H
Compound 247 S S Ph H p-C12H25—Ph—* H
Compound 248 S S Ph H p-C13H27—Ph—* H
Compound 249 S S Ph H p-C14H29—Ph—* H
Compound 250 S S Ph H p-C15H31—Ph—* H
Compound 251 S S Ph H p-C16H33—Ph—* H
Compound 252 S S Ph H p-C17H35—Ph—* H
Compound 253 S S Ph H p-C18H37—Ph—* H
Compound 254 S S
Figure US10497881-20191203-C00250
 		H p-C5H11—Ph—* H
Compound 255 S S
Figure US10497881-20191203-C00251
 		H p-C6H13—Ph—* H
Compound 256 S S
Figure US10497881-20191203-C00252
 		H p-C7H15—Ph—* H
Compound 257 S S
Figure US10497881-20191203-C00253
 		H p-C8H17—Ph—* H
Compound 258 S S
Figure US10497881-20191203-C00254
 		H p-C9H19—Ph—* H
Compound 259 S S
Figure US10497881-20191203-C00255
 		H p-C10H21—Ph—* H
Compound 260 S S
Figure US10497881-20191203-C00256
 		H p-C11H23—Ph—* H
Compound 261 S S
Figure US10497881-20191203-C00257
 		H p-C12H25—Ph—* H
Compound 262 S S
Figure US10497881-20191203-C00258
 		H p-C13H27—Ph—* H
Compound 263 S S
Figure US10497881-20191203-C00259
 		H p-C14H29—Ph—* H
TABLE 10
Xa1 Xa2 Ra11 Ra12 Ra21 Ra22
Compound 264 S S
Figure US10497881-20191203-C00260
 		H p-C15H31—Ph—* H
Compound 265 S S
Figure US10497881-20191203-C00261
 		H p-C16H33—Ph—* H
Compound 266 S S
Figure US10497881-20191203-C00262
 		H p-C17H35—Ph—* H
Compound 267 S S
Figure US10497881-20191203-C00263
 		H p-C18H37—Ph—* H
Compound 268 S S H H H p-C5H11—Ph—*
Compound 269 S S H H H p-C6H13—Ph—*
Compound 270 S S H H H p-C7H15—Ph—*
Compound 271 S S H H H p-C8H17—Ph—*
Compound 272 S S H H H p-C9H19—Ph—*
Compound 273 S S H H H p-C10H21—Ph—*
Compound 274 S S H H H p-C11H23—Ph—*
Compound 275 S S H H H p-C12H25—Ph—*
Compound 276 S S H H H p-C13H27—Ph—*
Compound 277 S S H H H p-C14H29—Ph—*
Compound 278 S S H H H p-C15H31—Ph—*
Compound 279 S S H H H p-C16H33—Ph—*
Compound 280 S S H H H p-C17H35—Ph—*
Compound 281 S S H H H p-C18H37—Ph—*
Compound 282 S S H H
Figure US10497881-20191203-C00264
 		H
Compound 283 S S H H
Figure US10497881-20191203-C00265
 		H
Compound 284 S S H H
Figure US10497881-20191203-C00266
 		H
Compound 285 S S H H
Figure US10497881-20191203-C00267
 		H
Compound 286 S S H H
Figure US10497881-20191203-C00268
 		H
Compound 287 S S H H
Figure US10497881-20191203-C00269
 		H
Compound 288 S S H H
Figure US10497881-20191203-C00270
 		H
Compound 289 S S H H
Figure US10497881-20191203-C00271
 		H
Compound 290 S S H H
Figure US10497881-20191203-C00272
 		H
TABLE 11
Xa1 Xa2 Ra11 Ra12 Ra21 Ra22
Com- pound 291 S S H H
Figure US10497881-20191203-C00273
 		H
Com- pound 292 S S H H
Figure US10497881-20191203-C00274
 		H
Com- pound 293 S S H H
Figure US10497881-20191203-C00275
 		H
Com- pound 294 S S H H
Figure US10497881-20191203-C00276
 		H
Com- pound 295 S S Ph H
Figure US10497881-20191203-C00277
 		H
Com- pound 296 S S Ph H
Figure US10497881-20191203-C00278
 		H
Com- pound 297 S S Ph H
Figure US10497881-20191203-C00279
 		H
Com- pound 298 S S Ph H
Figure US10497881-20191203-C00280
 		H
Com- pound 299 S S Ph H
Figure US10497881-20191203-C00281
 		H
Com- pound 300 S S Ph H
Figure US10497881-20191203-C00282
 		H
Com- pound 301 S S Ph H
Figure US10497881-20191203-C00283
 		H
Com- pound 302 S S Ph H
Figure US10497881-20191203-C00284
 		H
Com- pound 303 S S Ph H
Figure US10497881-20191203-C00285
 		H
Com- pound 304 S S Ph H
Figure US10497881-20191203-C00286
 		H
Com- pound 305 S S Ph H
Figure US10497881-20191203-C00287
 		H
Com- pound 306 S S Ph H
Figure US10497881-20191203-C00288
 		H
Com- pound 307 S S Ph H
Figure US10497881-20191203-C00289
 		H
Com- pound 308 S S
Figure US10497881-20191203-C00290
 		H
Figure US10497881-20191203-C00291
 		H
TABLE 12
Xa1 Xa2 Ra11 Ra12 Ra21 Ra22
Compound 309 S S
Figure US10497881-20191203-C00292
 		H
Figure US10497881-20191203-C00293
 		H
Compound 310 S S
Figure US10497881-20191203-C00294
 		H
Figure US10497881-20191203-C00295
 		H
Compound 311 S S
Figure US10497881-20191203-C00296
 		H
Figure US10497881-20191203-C00297
 		H
Compound 312 S S
Figure US10497881-20191203-C00298
 		H
Figure US10497881-20191203-C00299
 		H
Compound 313 S S
Figure US10497881-20191203-C00300
 		H
Figure US10497881-20191203-C00301
 		H
Compound 314 S S
Figure US10497881-20191203-C00302
 		H
Figure US10497881-20191203-C00303
 		H
Compound 315 S S
Figure US10497881-20191203-C00304
 		H
Figure US10497881-20191203-C00305
 		H
Compound 316 S S
Figure US10497881-20191203-C00306
 		H
Figure US10497881-20191203-C00307
 		H
Compound 317 S S
Figure US10497881-20191203-C00308
 		H
Figure US10497881-20191203-C00309
 		H
Compound 318 S S
Figure US10497881-20191203-C00310
 		H
Figure US10497881-20191203-C00311
 		H
Compound 319 S S
Figure US10497881-20191203-C00312
 		H
Figure US10497881-20191203-C00313
 		H
Compound 320 S S
Figure US10497881-20191203-C00314
 		H
Figure US10497881-20191203-C00315
 		H
Compound 321 S S H H H
Figure US10497881-20191203-C00316
Compound 322 S S H H H
Figure US10497881-20191203-C00317
Compound 323 S S H H H
Figure US10497881-20191203-C00318
Compound 324 S S H H H
Figure US10497881-20191203-C00319
Compound 325 S S H H H
Figure US10497881-20191203-C00320
Compound 326 S S H H H
Figure US10497881-20191203-C00321
TABLE 13
Xa1 Xa2 Ra11 Ra12 Ra21 Ra22
Compound 327 S S H H H
Figure US10497881-20191203-C00322
Compound 328 S S H H H
Figure US10497881-20191203-C00323
Compound 329 S S H H H
Figure US10497881-20191203-C00324
Compound 330 S S H H H
Figure US10497881-20191203-C00325
Compound 331 S S H H H
Figure US10497881-20191203-C00326
Compound 332 S S H H H
Figure US10497881-20191203-C00327
Compound 333 S S H H H
Figure US10497881-20191203-C00328
Compound 334 S S H H
Figure US10497881-20191203-C00329
 		H
Compound 335 S S H H
Figure US10497881-20191203-C00330
 		H
Compound 336 S S H H
Figure US10497881-20191203-C00331
 		H
Compound 337 S S H H
Figure US10497881-20191203-C00332
 		H
Compound 338 S S H H
Figure US10497881-20191203-C00333
 		H
Compound 339 S S H H
Figure US10497881-20191203-C00334
 		H
Compound 340 S S H H
Figure US10497881-20191203-C00335
 		H
Compound 341 S S H H
Figure US10497881-20191203-C00336
 		H
Compound 342 S S H H
Figure US10497881-20191203-C00337
 		H
Compound 343 S S H H
Figure US10497881-20191203-C00338
 		H
Compound 344 S S H H
Figure US10497881-20191203-C00339
 		H
TABLE 14
Xa1 Xa2 Ra11 Ra12 Ra21 Ra22
Compound 345 S S H H
Figure US10497881-20191203-C00340
 		H
Compound 346 S S H H
Figure US10497881-20191203-C00341
 		H
Compound 347 S S H H
Figure US10497881-20191203-C00342
 		H
Compound 348 S S Ph H
Figure US10497881-20191203-C00343
 		H
Compound 349 S S Ph H
Figure US10497881-20191203-C00344
 		H
Compound 350 S S Ph H
Figure US10497881-20191203-C00345
 		H
Compound 351 S S Ph H
Figure US10497881-20191203-C00346
 		H
Compound 352 S S Ph H
Figure US10497881-20191203-C00347
 		H
Compound 353 S S Ph H
Figure US10497881-20191203-C00348
 		H
Compound 354 S S Ph H
Figure US10497881-20191203-C00349
 		H
Compound 355 S S Ph H
Figure US10497881-20191203-C00350
 		H
Compound 356 S S Ph H
Figure US10497881-20191203-C00351
 		H
Compound 357 S S Ph H
Figure US10497881-20191203-C00352
 		H
Compound 358 S S Ph H
Figure US10497881-20191203-C00353
 		H
Compound 359 S S Ph H
Figure US10497881-20191203-C00354
 		H
Compound 360 S S Ph H
Figure US10497881-20191203-C00355
 		H
Compound 361 S S Ph H
Figure US10497881-20191203-C00356
 		H
Compound 362 S S
Figure US10497881-20191203-C00357
 		H
Figure US10497881-20191203-C00358
 		H
TABLE 15
Xa1 Xa2 Ra11 Ra12 Ra21 Ra22
Compound 363 S S
Figure US10497881-20191203-C00359
 		H
Figure US10497881-20191203-C00360
 		H
Compound 364 S S
Figure US10497881-20191203-C00361
 		H
Figure US10497881-20191203-C00362
 		H
Compound 365 S S
Figure US10497881-20191203-C00363
 		H
Figure US10497881-20191203-C00364
 		H
Compound 366 S S
Figure US10497881-20191203-C00365
 		H
Figure US10497881-20191203-C00366
 		H
Compound 367 S S
Figure US10497881-20191203-C00367
 		H
Figure US10497881-20191203-C00368
 		H
Compound 368 S S
Figure US10497881-20191203-C00369
 		H
Figure US10497881-20191203-C00370
 		H
Compound 369 S S
Figure US10497881-20191203-C00371
 		H
Figure US10497881-20191203-C00372
 		H
Compound 370 S S
Figure US10497881-20191203-C00373
 		H
Figure US10497881-20191203-C00374
 		H
Compound 371 S S
Figure US10497881-20191203-C00375
 		H
Figure US10497881-20191203-C00376
 		H
Compound 372 S S
Figure US10497881-20191203-C00377
 		H
Figure US10497881-20191203-C00378
 		H
Compound 373 S S
Figure US10497881-20191203-C00379
 		H
Figure US10497881-20191203-C00380
 		H
Compound 374 S S
Figure US10497881-20191203-C00381
 		H
Figure US10497881-20191203-C00382
 		H
Compound 375 S S
Figure US10497881-20191203-C00383
 		H
Figure US10497881-20191203-C00384
 		H
Compound 376 S S C10H21—* H p-C5H11—Ph—* H
Compound 377 S S C10H21—* H p-C6H13—Ph—* H
Compound 378 S S C10H21—* H p-C7H15—Ph—* H
Compound 379 S S C10H21—* H p-C8H17—Ph—* H
Compound 380 S S C10H21—* H p-C9H19—Ph—* H
Compound 381 S S C10H21—* H p-C10H21—Ph—* H
Compound 382 S S C10H21—* H p-C11H23—Ph—* H
Compound 383 S S C10H21—* H p-C12H25—Ph—* H
Compound 384 S S C10H21—* H p-C13H27—Ph—* H
Compound 385 S S C10H21—* H p-C14H29—Ph—* H
Compound 386 S S C10H21—* H p-C15H31—Ph—* H
Compound 387 S S C10H21—* H p-C16H33—Ph—* H
Compound 388 S S C10H21—* H p-C17H35—Ph—* H
Compound 389 S S C10H21—* H p-C18H37—Ph—* H
TABLE 16
Xa1 Xa2 Ra11 Ra12 Ra21 Ra22
Compound 390 S S C12H25—* H
Figure US10497881-20191203-C00385
 		H
Compound 391 S S C12H25—* H
Figure US10497881-20191203-C00386
 		H
Compound 392 S S C12H25—* H
Figure US10497881-20191203-C00387
 		H
Compound 393 S S C12H25—* H
Figure US10497881-20191203-C00388
 		H
Compound 394 S S C12H25—* H
Figure US10497881-20191203-C00389
 		H
Compound 395 S S C12H25—* H
Figure US10497881-20191203-C00390
 		H
Compound 396 S S C12H25—* H
Figure US10497881-20191203-C00391
 		H
Compound 397 S S C12H25—* H
Figure US10497881-20191203-C00392
 		H
Compound 398 S S C12H25—* H
Figure US10497881-20191203-C00393
 		H
Compound 399 S S C12H25—* H
Figure US10497881-20191203-C00394
 		H
Compound 400 S S C12H25—* H
Figure US10497881-20191203-C00395
 		H
Compound 401 S S C12H25—* H
Figure US10497881-20191203-C00396
 		H
Compound 402 S S C12H25—* H
Figure US10497881-20191203-C00397
 		H
Compound 403 S S C12H25—* H
Figure US10497881-20191203-C00398
 		H
Compound 404 S S C5H11—* H H C12H25—*
Compound 405 S S C6H13—* H H C12H25—*
Compound 406 S S C7H15—* H H C12H25—*
Compound 407 S S C8H17—* H H C12H25—*
Compound 408 S S C9H19—* H H C12H25—*
Compound 409 S S C10H21—* H H C12H25—*
Compound 410 S S C11H23—* H H C12H25—*
Compound 411 S S C12H25—* H H C12H25—*
Compound 412 S S C13H27—* H H C12H25—*
Compound 413 S S C14H29—* H H C12H25—*
Compound 414 S S C15H31—* H H C12H25—*
Compound 415 S S C16H33—* H H C12H25—*
Compound 416 S S C17H35—* H H C12H25—*
Compound 417 S S C18H37—* H H C12H25—*
TABLE 17
Xa1 Xa2 Ra11 Ra12 Ra21 Ra22
Compound 418 S S C10H21—* H H p-C5H11—Ph—*
Compound 419 S S C10H21—* H H p-C6H13—Ph—*
Compound 420 S S C10H21—* H H p-C7H15—Ph—*
Compound 421 S S C10H21—* H H p-C8H17—Ph—*
Compound 422 S S C10H21—* H H p-C9H19—Ph—*
Compound 423 S S C10H21—* H H p-C10H21—Ph—*
Compound 424 S S C10H21—* H H p-C11H23—Ph—*
Compound 425 S S C10H21—* H H p-C12H25—Ph—*
Compound 426 S S C10H21—* H H p-C13H27—Ph—*
Compound 427 S S C10H21—* H H p-C14H29—Ph—*
Compound 428 S S C10H21—* H H p-C15H31—Ph—*
Compound 429 S S C10H21—* H H p-C16H33—Ph—*
Compound 430 S S C10H21—* H H p-C17H35—Ph—*
Compound 431 S S C10H21—* H H p-C18H37—Ph—*
Compound 432 S S H C10H21—* H p-C5H11—Ph—*
Compound 433 S S H C10H21—* H p-C6H13—Ph—*
Compound 434 S S H C10H21—* H p-C7H15—Ph—*
Compound 435 S S H C10H21—* H p-C8H17—Ph—*
Compound 436 S S H C10H21—* H p-C9H19—Ph—*
Compound 437 S S H C10H21—* H p-C10H21—Ph—*
Compound 438 S S H C10H21—* H p-C11H23—Ph—*
Compound 439 S S H C10H21—* H p-C12H25—Ph—*
Compound 440 S S H C10H21—* H p-C13H27—Ph—*
Compound 441 S S H C10H21—* H p-C14H29—Ph—*
Compound 442 S S H C10H21—* H p-C15H31—Ph—*
Compound 443 S S H C10H21—* H p-C16H33—Ph—*
Compound 444 S S H C10H21—* H p-C17H35—Ph—*
Compound 445 S S H C10H21—* H p-C18H37—Ph—*
Compound 446 S S
Figure US10497881-20191203-C00399
 		H
Figure US10497881-20191203-C00400
 		H
Compound 447 S S
Figure US10497881-20191203-C00401
 		H
Figure US10497881-20191203-C00402
 		H
Compound 448 S S
Figure US10497881-20191203-C00403
 		H
Figure US10497881-20191203-C00404
 		H
Compound 449 S S
Figure US10497881-20191203-C00405
 		H
Figure US10497881-20191203-C00406
 		H
Compound 450 S S
Figure US10497881-20191203-C00407
 		H
Figure US10497881-20191203-C00408
 		H
Compound 451 S S
Figure US10497881-20191203-C00409
 		H
Figure US10497881-20191203-C00410
 		H
Compound 452 S S
Figure US10497881-20191203-C00411
 		H
Figure US10497881-20191203-C00412
 		H
Compound 453 S S
Figure US10497881-20191203-C00413
 		H
Figure US10497881-20191203-C00414
 		H
TABLE 18
Xa1 Xa2 Ra11 Ra12 Ra21 Ra22
Compound 454 S S
Figure US10497881-20191203-C00415
 		H
Figure US10497881-20191203-C00416
 		H
Compound 455 S S
Figure US10497881-20191203-C00417
 		H
Figure US10497881-20191203-C00418
 		H
Compound 456 S S
Figure US10497881-20191203-C00419
 		H
Figure US10497881-20191203-C00420
 		H
Compound 457 S S
Figure US10497881-20191203-C00421
 		H
Figure US10497881-20191203-C00422
 		H
Compound 458 S S
Figure US10497881-20191203-C00423
 		H
Figure US10497881-20191203-C00424
 		H
Compound 459 S S
Figure US10497881-20191203-C00425
 		H
Figure US10497881-20191203-C00426
 		H
Compound 460 S S
Figure US10497881-20191203-C00427
 		H
Figure US10497881-20191203-C00428
 		H
Compound 461 S S
Figure US10497881-20191203-C00429
 		H
Figure US10497881-20191203-C00430
 		H
Compound 462 S S
Figure US10497881-20191203-C00431
 		H
Figure US10497881-20191203-C00432
 		H
Compound 463 S S
Figure US10497881-20191203-C00433
 		H
Figure US10497881-20191203-C00434
 		H
Compound 464 S S
Figure US10497881-20191203-C00435
 		H
Figure US10497881-20191203-C00436
 		H
Compound 465 S S
Figure US10497881-20191203-C00437
 		H
Figure US10497881-20191203-C00438
 		H
Compound 466 S S
Figure US10497881-20191203-C00439
 		H
Figure US10497881-20191203-C00440
 		H
Compound 467 S S
Figure US10497881-20191203-C00441
 		H
Figure US10497881-20191203-C00442
 		H
Compound 468 S S
Figure US10497881-20191203-C00443
 		H
Figure US10497881-20191203-C00444
 		H
Compound 469 S S
Figure US10497881-20191203-C00445
 		H
Figure US10497881-20191203-C00446
 		H
Compound 470 S S
Figure US10497881-20191203-C00447
 		H
Figure US10497881-20191203-C00448
 		H
Compound 471 S S
Figure US10497881-20191203-C00449
 		H
Figure US10497881-20191203-C00450
 		H
TABLE 19
Xa1 Xa2 Ra11 Ra12 Ra21 Ra22
Compound 472 S S
Figure US10497881-20191203-C00451
 		H
Figure US10497881-20191203-C00452
 		H
Compound 473 S S
Figure US10497881-20191203-C00453
 		H
Figure US10497881-20191203-C00454
 		H
Compound 474 S S
Figure US10497881-20191203-C00455
 		H
Figure US10497881-20191203-C00456
 		H
Compound 475 S S
Figure US10497881-20191203-C00457
 		H
Figure US10497881-20191203-C00458
 		H
Compound 476 S S
Figure US10497881-20191203-C00459
 		H
Figure US10497881-20191203-C00460
 		H
Compound 477 S S
Figure US10497881-20191203-C00461
 		H
Figure US10497881-20191203-C00462
 		H
Compound 478 S S
Figure US10497881-20191203-C00463
 		H
Figure US10497881-20191203-C00464
 		H
Compound 479 S S
Figure US10497881-20191203-C00465
 		H
Figure US10497881-20191203-C00466
 		H
Compound 480 S S
Figure US10497881-20191203-C00467
 		H
Figure US10497881-20191203-C00468
 		H
Compound 481 S S
Figure US10497881-20191203-C00469
 		H
Figure US10497881-20191203-C00470
 		H
Compound 482 S S
Figure US10497881-20191203-C00471
 		H
Figure US10497881-20191203-C00472
 		H
Compound 483 S S
Figure US10497881-20191203-C00473
 		H
Figure US10497881-20191203-C00474
 		H
Compound 484 S S
Figure US10497881-20191203-C00475
 		H
Figure US10497881-20191203-C00476
 		H
Compound 485 S S
Figure US10497881-20191203-C00477
 		H
Figure US10497881-20191203-C00478
 		H
Compound 486 S S
Figure US10497881-20191203-C00479
 		H
Figure US10497881-20191203-C00480
 		H
Compound 487 O O C5H11—* H C5H11—* H
Compound 488 O O C6H13—* H C6H13—* H
Compound 489 O O C7H15—* H C7H15—* H
Compound 490 O O C8H17—* H C8H17—* H
Compound 491 O O C9H19—* H C9H19—* H
Compound 492 O O C10H21—* H C10H21—* H
Compound 493 O O C11H23—* H C11H23—* H
Compound 494 O O C12H25—* H C12H25—* H
Compound 495 O O C13H27—* H C13H27—* H
Compound 496 O O C14H29—* H C14H29—* H
Compound 497 O O C15H31—* H C15H31—* H
TABLE 20
Xa1 Xa2 Ra11 Ra12 Ra21 Ra22
Compound 498 O O C16H33—* H C16H33—* H
Compound 499 O O C17H35—* H C17H35—* H
Compound 500 O O C18H37—* H C18H37—* H
Compound 501 O O p-C5H11—Ph—* H p-C5H11—Ph—* H
Compound 502 O O p-C6H13—Ph—* H p-C6H13—Ph—* H
Compound 503 O O p-C7H15—Ph—* H p-C7H15—Ph—* H
Compound 504 O O p-C8H17—Ph—* H p-C8H17—Ph—* H
Compound 505 O O p-C9H19—Ph—* H p-C9H19—Ph—* H
Compound 506 O O p-C10H21—Ph—* H p-C10H21—Ph—* H
Compound 507 O O p-C11H23—Ph—* H p-C11H23—Ph—* H
Compound 508 O O p-C12H25—Ph—* H p-C12H25—Ph—* H
Compound 509 O O p-C13H27—Ph—* H p-C13H27—Ph—* H
Compound 510 O O p-C14H29—Ph—* H p-C14H29—Ph—* H
Compound 511 O O p-C15H31—Ph—* H p-C15H31—Ph—* H
Compound 512 O O p-C16H33—Ph—* H p-C16H33—Ph—* H
Compound 513 O O p-C17H35—Ph—* H p-C17H35—Ph—* H
Compound 514 O O p-C18H37—Ph—* H p-C18H37—Ph—* H
Compound 515 O O
Figure US10497881-20191203-C00481
 		H
Figure US10497881-20191203-C00482
 		H
Compound 516 O O
Figure US10497881-20191203-C00483
 		H
Figure US10497881-20191203-C00484
 		H
Compound 517 O O
Figure US10497881-20191203-C00485
 		H
Figure US10497881-20191203-C00486
 		H
Compound 518 O O
Figure US10497881-20191203-C00487
 		H
Figure US10497881-20191203-C00488
 		H
Compound 519 O O
Figure US10497881-20191203-C00489
 		H
Figure US10497881-20191203-C00490
 		H
Compound 520 O O
Figure US10497881-20191203-C00491
 		H
Figure US10497881-20191203-C00492
 		H
Compound 521 O O
Figure US10497881-20191203-C00493
 		H
Figure US10497881-20191203-C00494
 		H
Compound 522 O O
Figure US10497881-20191203-C00495
 		H
Figure US10497881-20191203-C00496
 		H
Compound 523 O O
Figure US10497881-20191203-C00497
 		H
Figure US10497881-20191203-C00498
 		H
Compound 524 O O
Figure US10497881-20191203-C00499
 		H
Figure US10497881-20191203-C00500
 		H
Compound 525 O O
Figure US10497881-20191203-C00501
 		H
Figure US10497881-20191203-C00502
 		H
Compound 526 O O
Figure US10497881-20191203-C00503
 		H
Figure US10497881-20191203-C00504
 		H
TABLE 21
Xa1 Xa2 Ra11 Ra12 Ra21 Ra22
Compound 527 O O
Figure US10497881-20191203-C00505
 		H
Figure US10497881-20191203-C00506
 		H
Compound 528 O O
Figure US10497881-20191203-C00507
 		H
Figure US10497881-20191203-C00508
 		H
Compound 529 S S C4H9OC4H8—* H C4H9OC4H8—* H
Compound 530 S S C2H5OC2H4—* H C2H5OC2H4—* H
Compound 531 S S C6H13OC4H8—* H C6H13OC4H8—* H
Compound 532 S S C2H5OC4H8—* H C2H5OC4H8—* H
Compound 533 S S CH3OC3H6—* H CH3OC3H6—* H
Compound 534 S S
Figure US10497881-20191203-C00509
 		H
Figure US10497881-20191203-C00510
 		H
Compound 535 S S
Figure US10497881-20191203-C00511
 		H
Figure US10497881-20191203-C00512
 		H
Compound 536 S S
Figure US10497881-20191203-C00513
 		H
Figure US10497881-20191203-C00514
 		H
Compound 537 S S PhC3H6—* H PhC3H6—* H
Compound 538 S S PhOC3H6—* H PhOC3H6—* H
Compound 539 S S
Figure US10497881-20191203-C00515
 		H
Figure US10497881-20191203-C00516
 		H
Compound 540 S S
Figure US10497881-20191203-C00517
 		H
Figure US10497881-20191203-C00518
 		H
Compound 541 S S
Figure US10497881-20191203-C00519
 		H
Figure US10497881-20191203-C00520
 		H
Compound 542 S S
Figure US10497881-20191203-C00521
 		H
Figure US10497881-20191203-C00522
 		H
Compound 543 S S
Figure US10497881-20191203-C00523
 		H
Figure US10497881-20191203-C00524
 		H
Compound 544 S S 3,7-Dimethyloctyl H 3,7-Dimethyloctyl H
TABLE 22
Xa1 Xa2 Ra11 Ra12 Ra21 Ra22
Compound S S 3,7-Dimethyloctyl H H H
545
Compound S S 2-Ethylhexyl H 2-Ethylhexyl H
546
Compound 547 S S
Figure US10497881-20191203-C00525
 		H
Figure US10497881-20191203-C00526
 		H
Compound 548 S S
Figure US10497881-20191203-C00527
 		H
Figure US10497881-20191203-C00528
 		H
Compound 549 S S
Figure US10497881-20191203-C00529
 		H
Figure US10497881-20191203-C00530
 		H
Compound 550 S S
Figure US10497881-20191203-C00531
 		H H H
Compound 551 S S
Figure US10497881-20191203-C00532
 		H
Figure US10497881-20191203-C00533
 		H
Compound 552 S S C5H11—* H
Figure US10497881-20191203-C00534
 		H
Compound 553 S S
Figure US10497881-20191203-C00535
 		H
Figure US10497881-20191203-C00536
 		H
Compound 554 S S
Figure US10497881-20191203-C00537
 		H
Figure US10497881-20191203-C00538
 		H
Compound 555 S S
Figure US10497881-20191203-C00539
 		H
Figure US10497881-20191203-C00540
 		H
Compound 556 S S
Figure US10497881-20191203-C00541
 		H
Figure US10497881-20191203-C00542
 		H
Compound 557 S S
Figure US10497881-20191203-C00543
 		H
Figure US10497881-20191203-C00544
 		H
Compound 558 S S
Figure US10497881-20191203-C00545
 		H H H
Compound 559 S S
Figure US10497881-20191203-C00546
 		H
Figure US10497881-20191203-C00547
 		H
Compound 560 S S
Figure US10497881-20191203-C00548
 		H
Figure US10497881-20191203-C00549
 		H
Compound 561 S S
Figure US10497881-20191203-C00550
 		H
Figure US10497881-20191203-C00551
 		H
Compound 562 S S
Figure US10497881-20191203-C00552
 		H
Figure US10497881-20191203-C00553
 		H
TABLE 23
Xb1 Xb2 Rb11 Rb12 Rb21 Rb22
Compound 563 S S C5H11—* H C5H11—* H
Compound 564 S S C6H13—* H C6H13—* H
Compound 565 S S C7H15—* H C7H15—* H
Compound 566 S S C8H17—* H C8H17—* H
Compound 567 S S C9H19—* H C9H19—* H
Compound 568 S S C10H21—* H C10H21—* H
Compound 569 S S C11H23—* H C11H23—* H
Compound 570 S S C12H25—* H C12H25—* H
Compound 571 S S C13H27—* H C13H27—* H
Compound 572 S S C14H29—* H C14H29—* H
Compound 573 S S C15H31—* H C15H31—* H
Compound 574 S S C16H33—* H C16H33—* H
Compound 575 S S C17H35—* H C17H35—* H
Compound 576 S S C18H37—* H C18H37—* H
Compound 577 S S C5H11—* C5H11—* C5H11—* C5H11—*
Compound 578 S S C6H13—* C6H13—* C6H13—* C6H13—*
Compound 579 S S C7H15—* C7H15—* C7H15—* C7H15—*
Compound 580 S S C8H17—* C8H17—* C8H17—* C8H17—*
Compound 581 S S C9H19—* C9H19—* C9H19—* C9H19—*
Compound 582 S S C10H21—* C10H21—* C10H21—* C10H21—*
Compound 583 S S C11H23—* C11H23—* C11H23—* C11H23—*
Compound 584 S S C12H25—* C12H25—* C12H25—* C12H25—*
Compound 585 S S C13H27—* C13H27—* C13H27—* C13H27—*
Compound 586 S S C14H29—* C14H29—* C14H29—* C14H29—*
Compound 587 S S C15H31—* C15H31—* C15H31—* C15H31—*
Compound 588 S S C16H33—* C16H33—* C16H33—* C16H33—*
Compound 589 S S C17H35—* C17H35—* C17H35—* C17H35—*
Compound 590 S S C18H37—* C18H37—* C18H37—* C18H37—*
Compound 591 S S p-C5H11—Ph—* H p-C5H11—Ph—* H
Compound 592 S S p-C6H13—Ph—* H p-C6H13—Ph—* H
Compound 593 S S p-C7H15—Ph—* H p-C7H15—Ph—* H
Compound 594 S S p-C8H17—Ph—* H p-C8H17—Ph—* H
Compound 595 S S p-C9H19—Ph—* H p-C9H19—Ph—* H
Compound 596 S S p-C10H21—Ph—* H p-C10H21—Ph—* H
Compound 597 S S p-C11H23—Ph—* H p-C11H23—Ph—* H
Compound 598 S S p-C12H25—Ph—* H p-C12H25—Ph—* H
Compound 599 S S p-C13H27—Ph—* H p-C13H27—Ph—* H
Compound 600 S S p-C14H29—Ph—* H p-C14H29—Ph—* H
Compound 601 S S p-C15H31—Ph—* H p-C15H31—Ph—* H
Compound 602 S S p-C16H33—Ph—* H p-C16H33—Ph—* H
Compound 603 S S p-C17H35—Ph—* H p-C17H35—Ph—* H
Compound 604 S S p-C18H37—Ph—* H p-C18H37—Ph—* H
Compound 605 S S p-C5H11—Ph—* p-C5H11—Ph—* p-C5H11—Ph—* p-C5H11—Ph—*
Compound 606 S S p-C6H13—Ph—* p-C6H13—Ph—* p-C6H13—Ph—* p-C6H13—Ph—*
Compound 607 S S p-C7H15—Ph—* p-C7H15—Ph—* p-C7H15—Ph—* p-C7H15—Ph—*
Compound 608 S S p-C8H17—Ph—* p-C8H17—Ph—* p-C8H17—Ph—* p-C8H17—Ph—*
Compound 609 S S p-C9H19—Ph—* p-C9H19—Ph—* p-C9H19—Ph—* p-C9H19—Ph—*
Compound 610 S S p-C10H21—Ph—* p-C10H21—Ph—* p-C10H21—Ph—* p-C10H21—Ph—*
Compound 611 S S p-C11H23—Ph—* p-C11H23—Ph—* p-C11H23—Ph—* p-C11H23—Ph—*
Compound 612 S S p-C12H25—Ph—* p-C12H25—Ph—* p-C12H25—Ph—* p-C12H25—Ph—*
Compound 613 S S p-C13H27—Ph—* p-C13H27—Ph—* p-C13H27—Ph—* p-C13H27—Ph—*
TABLE 24
Xa1 Xa2 Ra11 Ra12 Ra21 Ra22
Compound 614 S S p-C14H29—Ph—* p-C14H29—Ph—* p-C14H29—Ph—* p-C14H29—Ph—*
Compound 615 S S p-C15H31—Ph—* p-C15H31—Ph—* p-C15H31—Ph—* p-C15H31—Ph—*
Compound 616 S S p-C16H33—Ph—* p-C16H33—Ph—* p-C16H33—Ph—* p-C16H33—Ph—*
Compound 617 S S p-C17H35—Ph—* p-C17H35—Ph—* p-C17H35—Ph—* p-C17H35—Ph—*
Compound 618 S S p-C18H37—Ph—* p-C18H37—Ph—* p-C18H37—Ph—* p-C18H37—Ph—*
Compound 619 S S
Figure US10497881-20191203-C00554
 		H
Figure US10497881-20191203-C00555
 		H
Compound 620 S S
Figure US10497881-20191203-C00556
 		H
Figure US10497881-20191203-C00557
 		H
Compound 621 S S
Figure US10497881-20191203-C00558
 		H
Figure US10497881-20191203-C00559
 		H
Compound 622 S S
Figure US10497881-20191203-C00560
 		H
Figure US10497881-20191203-C00561
 		H
Compound 623 S S
Figure US10497881-20191203-C00562
 		H
Figure US10497881-20191203-C00563
 		H
Compound 624 S S
Figure US10497881-20191203-C00564
 		H
Figure US10497881-20191203-C00565
 		H
Compound 625 S S
Figure US10497881-20191203-C00566
 		H
Figure US10497881-20191203-C00567
 		H
Compound 626 S S
Figure US10497881-20191203-C00568
 		H
Figure US10497881-20191203-C00569
 		H
Compound 627 S S
Figure US10497881-20191203-C00570
 		H
Figure US10497881-20191203-C00571
 		H
Compound 628 S S
Figure US10497881-20191203-C00572
 		H
Figure US10497881-20191203-C00573
 		H
Compound 629 S S
Figure US10497881-20191203-C00574
 		H
Figure US10497881-20191203-C00575
 		H
Compound 630 S S
Figure US10497881-20191203-C00576
 		H
Figure US10497881-20191203-C00577
 		H
Compound 631 S S
Figure US10497881-20191203-C00578
 		H
Figure US10497881-20191203-C00579
 		H
Compound 632 S S
Figure US10497881-20191203-C00580
 		H
Figure US10497881-20191203-C00581
 		H
Compound 633 S S
Figure US10497881-20191203-C00582
Figure US10497881-20191203-C00583
Figure US10497881-20191203-C00584
Figure US10497881-20191203-C00585
Compound 634 S S
Figure US10497881-20191203-C00586
Figure US10497881-20191203-C00587
Figure US10497881-20191203-C00588
Figure US10497881-20191203-C00589
Compound 635 S S
Figure US10497881-20191203-C00590
Figure US10497881-20191203-C00591
Figure US10497881-20191203-C00592
Figure US10497881-20191203-C00593
TABLE 25
Xa1 Xa2 Ra11 Ra12 Ra21 Ra22
Compound 636 S S
Figure US10497881-20191203-C00594
Figure US10497881-20191203-C00595
Figure US10497881-20191203-C00596
Figure US10497881-20191203-C00597
Compound 637 S S
Figure US10497881-20191203-C00598
Figure US10497881-20191203-C00599
Figure US10497881-20191203-C00600
Figure US10497881-20191203-C00601
Compound 638 S S
Figure US10497881-20191203-C00602
Figure US10497881-20191203-C00603
Figure US10497881-20191203-C00604
Figure US10497881-20191203-C00605
Compound 639 S S
Figure US10497881-20191203-C00606
Figure US10497881-20191203-C00607
Figure US10497881-20191203-C00608
Figure US10497881-20191203-C00609
Compound 640 S S
Figure US10497881-20191203-C00610
Figure US10497881-20191203-C00611
Figure US10497881-20191203-C00612
Figure US10497881-20191203-C00613
Compound 641 S S
Figure US10497881-20191203-C00614
Figure US10497881-20191203-C00615
Figure US10497881-20191203-C00616
Figure US10497881-20191203-C00617
Compound 642 S S
Figure US10497881-20191203-C00618
Figure US10497881-20191203-C00619
Figure US10497881-20191203-C00620
Figure US10497881-20191203-C00621
Compound 643 S S
Figure US10497881-20191203-C00622
Figure US10497881-20191203-C00623
Figure US10497881-20191203-C00624
Figure US10497881-20191203-C00625
Compound 644 S S
Figure US10497881-20191203-C00626
Figure US10497881-20191203-C00627
Figure US10497881-20191203-C00628
Figure US10497881-20191203-C00629
Compound 645 S S
Figure US10497881-20191203-C00630
Figure US10497881-20191203-C00631
Figure US10497881-20191203-C00632
Figure US10497881-20191203-C00633
Compound 646 S S
Figure US10497881-20191203-C00634
Figure US10497881-20191203-C00635
Figure US10497881-20191203-C00636
Figure US10497881-20191203-C00637
Compound 647 S S
Figure US10497881-20191203-C00638
 		H
Figure US10497881-20191203-C00639
 		H
Compound 648 S S
Figure US10497881-20191203-C00640
 		H
Figure US10497881-20191203-C00641
 		H
Compound 649 S S
Figure US10497881-20191203-C00642
 		H
Figure US10497881-20191203-C00643
 		H
Compound 650 S S
Figure US10497881-20191203-C00644
 		H
Figure US10497881-20191203-C00645
 		H
Compound 651 S S
Figure US10497881-20191203-C00646
 		H
Figure US10497881-20191203-C00647
 		H
Compound 652 S S
Figure US10497881-20191203-C00648
 		H
Figure US10497881-20191203-C00649
 		H
Compound 653 S S
Figure US10497881-20191203-C00650
 		H
Figure US10497881-20191203-C00651
 		H
TABLE 26
Xa1 Xa2 Ra11 Ra12 Ra21 Ra22
Compound 654 S S
Figure US10497881-20191203-C00652
 		H
Figure US10497881-20191203-C00653
 		H
Compound 655 S S
Figure US10497881-20191203-C00654
 		H
Figure US10497881-20191203-C00655
 		H
Compound 656 S S
Figure US10497881-20191203-C00656
 		H
Figure US10497881-20191203-C00657
 		H
Compound 657 S S
Figure US10497881-20191203-C00658
 		H
Figure US10497881-20191203-C00659
 		H
Compound 658 S S
Figure US10497881-20191203-C00660
 		H
Figure US10497881-20191203-C00661
 		H
Compound 659 S S
Figure US10497881-20191203-C00662
 		H
Figure US10497881-20191203-C00663
 		H
Compound 660 S S
Figure US10497881-20191203-C00664
 		H
Figure US10497881-20191203-C00665
 		H
Compound 661 S S
Figure US10497881-20191203-C00666
Figure US10497881-20191203-C00667
Figure US10497881-20191203-C00668
Figure US10497881-20191203-C00669
Compound 662 S S
Figure US10497881-20191203-C00670
Figure US10497881-20191203-C00671
Figure US10497881-20191203-C00672
Figure US10497881-20191203-C00673
Compound 663 S S
Figure US10497881-20191203-C00674
Figure US10497881-20191203-C00675
Figure US10497881-20191203-C00676
Figure US10497881-20191203-C00677
Compound 664 S S
Figure US10497881-20191203-C00678
Figure US10497881-20191203-C00679
Figure US10497881-20191203-C00680
Figure US10497881-20191203-C00681
Compound 665 S S
Figure US10497881-20191203-C00682
Figure US10497881-20191203-C00683
Figure US10497881-20191203-C00684
Figure US10497881-20191203-C00685
Compound 666 S S
Figure US10497881-20191203-C00686
Figure US10497881-20191203-C00687
Figure US10497881-20191203-C00688
Figure US10497881-20191203-C00689
Compound 667 S S
Figure US10497881-20191203-C00690
Figure US10497881-20191203-C00691
Figure US10497881-20191203-C00692
Figure US10497881-20191203-C00693
Compound 668 S S
Figure US10497881-20191203-C00694
Figure US10497881-20191203-C00695
Figure US10497881-20191203-C00696
Figure US10497881-20191203-C00697
Compound 669 S S
Figure US10497881-20191203-C00698
Figure US10497881-20191203-C00699
Figure US10497881-20191203-C00700
Figure US10497881-20191203-C00701
Compound 670 S S
Figure US10497881-20191203-C00702
Figure US10497881-20191203-C00703
Figure US10497881-20191203-C00704
Figure US10497881-20191203-C00705
Compound 671 S S
Figure US10497881-20191203-C00706
Figure US10497881-20191203-C00707
Figure US10497881-20191203-C00708
Figure US10497881-20191203-C00709
TABLE 27
Xa1 Xa2 Ra11 Ra12 Ra21 Ra22
Compound 672 S S
Figure US10497881-20191203-C00710
Figure US10497881-20191203-C00711
Figure US10497881-20191203-C00712
Figure US10497881-20191203-C00713
Compound 673 S S
Figure US10497881-20191203-C00714
Figure US10497881-20191203-C00715
Figure US10497881-20191203-C00716
Figure US10497881-20191203-C00717
Compound 674 S S
Figure US10497881-20191203-C00718
Figure US10497881-20191203-C00719
Figure US10497881-20191203-C00720
Figure US10497881-20191203-C00721
Compound 675 S S H C5H11—* H C5H11—*
Compound 676 S S H C6H13—* H C6H13—*
Compound 677 S S H C7H15—* H C7H15—*
Compound 678 S S H C8H17—* H C8H17—*
Compound 679 S S H C9H19—* H C9H19—*
Compound 680 S S H C10H21—* H C10H21—*
Compound 681 S S H C11H23—* H C11H23—*
Compound 682 S S H C12H25—* H C12H25—*
Compound 683 S S H C13H27—* H C13H27—*
Compound 684 S S H C14H29—* H C14H29—*
Compound 685 S S H C15H31—* H C15H31—*
Compound 686 S S H C16H33—* H C16H33—*
Compound 687 S S H C17H35—* H C17H35—*
Compound 688 S S H C18H37—* H C18H37—*
Compound 689 S S H p-C5H11—Ph—* H p-C5H11—Ph—*
Compound 690 S S H p-C6H13—Ph—* H p-C6H13—Ph—*
Compound 691 S S H p-C7H15—Ph—* H p-C7H15—Ph—*
Compound 692 S S H p-C8H17—Ph—* H p-C8H17—Ph—*
Compound 693 S S H p-C9H19—Ph—* H p-C9H19—Ph—*
Compound 694 S S H p-C10H21—Ph—* H p-C10H21—Ph—*
Compound 695 S S H p-C11H23—Ph—* H p-C11H23—Ph—*
Compound 696 S S H p-C12H25—Ph—* H p-C12H25—Ph—*
Compound 697 S S H p-C13H27—Ph—* H p-C13H27—Ph—*
Compound 698 S S H p-C14H29—Ph—* H p-C14H29—Ph—*
Compound 699 S S H p-C15H31—Ph—* H p-C15H31—Ph—*
Compound 700 S S H p-C16H33—Ph—* H p-C16H33—Ph—*
Compound 701 S S H p-C17H35—Ph—* H p-C17H35—Ph—*
Compound 702 S S H p-C18H37—Ph—* H p-C18H37—Ph—*
Compound 703 S S H
Figure US10497881-20191203-C00722
 		H
Figure US10497881-20191203-C00723
Compound 704 S S H
Figure US10497881-20191203-C00724
 		H
Figure US10497881-20191203-C00725
Compound 705 S S H
Figure US10497881-20191203-C00726
 		H
Figure US10497881-20191203-C00727
Compound 706 S S H
Figure US10497881-20191203-C00728
 		H
Figure US10497881-20191203-C00729
Compound 707 S S H
Figure US10497881-20191203-C00730
 		H
Figure US10497881-20191203-C00731
TABLE 28
Xa1 Xa2 Ra11 Ra12 Ra21 Ra22
Compound 708 S S H
Figure US10497881-20191203-C00732
 		H
Figure US10497881-20191203-C00733
Compound 709 S S H
Figure US10497881-20191203-C00734
 		H
Figure US10497881-20191203-C00735
Compound 710 S S H
Figure US10497881-20191203-C00736
 		H
Figure US10497881-20191203-C00737
Compound 711 S S H
Figure US10497881-20191203-C00738
 		H
Figure US10497881-20191203-C00739
Compound 712 S S H
Figure US10497881-20191203-C00740
 		H
Figure US10497881-20191203-C00741
Compound 713 S S H
Figure US10497881-20191203-C00742
 		H
Figure US10497881-20191203-C00743
Compound 714 S S H
Figure US10497881-20191203-C00744
 		H
Figure US10497881-20191203-C00745
Compound 715 S S H
Figure US10497881-20191203-C00746
 		H
Figure US10497881-20191203-C00747
Compound 716 S S H
Figure US10497881-20191203-C00748
 		H
Figure US10497881-20191203-C00749
Compound 717 S S H H C5H11—* H
Compound 718 S S H H C6H13—* H
Compound 719 S S H H C7H15—* H
Compound 720 S S H H C8H17—* H
Compound 721 S S H H C9H19—* H
Compound 722 S S H H C10H21—* H
Compound 723 S S H H C11H23—* H
Compound 724 S S H H C12H25—* H
Compound 725 S S H H C13H27—* H
Compound 726 S S H H C14H29—* H
Compound 727 S S H H C15H31—* H
Compound 728 S S H H C16H33—* H
Compound 729 S S H H C17H35—* H
Compound 730 S S H H C18H37—* H
Compound 731 S S Ph H C5H11—* H
Compound 732 S S Ph H C6H13—* H
Compound 733 S S Ph H C7H15—* H
Compound 734 S S Ph H C8H17—* H
Compound 735 S S Ph H C9H19—* H
Compound 736 S S Ph H C10H21—* H
Compound 737 S S Ph H C11H23—* H
Compound 738 S S Ph H C12H25—* H
Compound 739 S S Ph H C13H27—* H
Compound 740 S S Ph H C14H29—* H
Compound 741 S S Ph H C15H31—* H
Compound 742 S S Ph H C16H33—* H
Compound 743 S S Ph H C17H35—* H
TABLE 29
Xa1 Xa2 Ra11 Ra12 Ra21 Ra22
Compound 744 S S Ph H C18H37—* H
Compound 745 S S
Figure US10497881-20191203-C00750
 		H C5H11—* H
Compound 746 S S
Figure US10497881-20191203-C00751
 		H C6H13—* H
Compound 747 S S
Figure US10497881-20191203-C00752
 		H C7H15—* H
Compound 748 S S
Figure US10497881-20191203-C00753
 		H C8H17—* H
Compound 749 S S
Figure US10497881-20191203-C00754
 		H C9H19—* H
Compound 750 S S
Figure US10497881-20191203-C00755
 		H C10H21—* H
Compound 751 S S
Figure US10497881-20191203-C00756
 		H C11H23—* H
Compound 752 S S
Figure US10497881-20191203-C00757
 		H C12H25—* H
Compound 753 S S
Figure US10497881-20191203-C00758
 		H C13H27—* H
Compound 754 S S
Figure US10497881-20191203-C00759
 		H C14H29—* H
Compound 755 S S
Figure US10497881-20191203-C00760
 		H C15H31—* H
Compound 756 S S
Figure US10497881-20191203-C00761
 		H C16H33—* H
Compound 757 S S
Figure US10497881-20191203-C00762
 		H C17H35—* H
Compound 758 S S
Figure US10497881-20191203-C00763
 		H C18H37—* H
Compound 759 S S H H H C5H11—*
Compound 760 S S H H H C6H13—*
Compound 761 S S H H H C7H15—*
Compound 762 S S H H H C8H17—*
Compound 763 S S H H H C9H19—*
Compound 764 S S H H H C10H21—*
Compound 765 S S H H H C11H23—*
Compound 766 S S H H H C12H25—*
Compound 767 S S H H H C13H27—*
Compound 768 S S H H H C14H29—*
Compound 769 S S H H H C15H31—*
Compound 770 S S H H H C16H33—*
Compound 771 S S H H H C17H35—*
TABLE 30
Xb1 Xb2 Rb11 Rb12 Rb21 Rb22
Compound 772 S S H H H C18H37—*
Compound 773 S S H H p-C5H11—Ph—* H
Compound 774 S S H H p-C6H13—Ph—* H
Compound 775 S S H H p-C7H15—Ph—* H
Compound 776 S S H H p-C8H17—Ph—* H
Compound 777 S S H H p-C9H19—Ph—* H
Compound 778 S S H H p-C10H21—Ph—* H
Compound 779 S S H H p-C11H23—Ph—* H
Compound 780 S S H H p-C12H25—Ph—* H
Compound 781 S S H H p-C13H27—Ph—* H
Compound 782 S S H H p-C14H29—Ph—* H
Compound 783 S S H H p-C15H31—Ph—* H
Compound 784 S S H H p-C16H33—Ph—* H
Compound 785 S S H H p-C17H35—Ph—* H
Compound 786 S S H H p-C18H37—Ph—* H
Compound 787 S S Ph H p-C5H11—Ph—* H
Compound 788 S S Ph H p-C6H13—Ph—* H
Compound 789 S S Ph H p-C7H15—Ph—* H
Compound 790 S S Ph H p-C8H17—Ph—* H
Compound 791 S S Ph H p-C9H19—Ph—* H
Compound 792 S S Ph H p-C10H21—Ph—* H
Compound 793 S S Ph H p-C11H23—Ph—* H
Compound 794 S S Ph H p-C12H25—Ph—* H
Compound 795 S S Ph H p-C13H27—Ph—* H
Compound 796 S S Ph H p-C14H29—Ph—* H
Compound 797 S S Ph H p-C15H31—Ph—* H
Compound 798 S S Ph H p-C16H33—Ph—* H
Compound 799 S S Ph H p-C17H35—Ph—* H
Compound 800 S S Ph H p-C18H37—Ph—* H
Compound 801 S S
Figure US10497881-20191203-C00764
 		H p-C5H11—Ph—* H
Compound 802 S S
Figure US10497881-20191203-C00765
 		H p-C6H13—Ph—* H
Compound 803 S S
Figure US10497881-20191203-C00766
 		H p-C7H15—Ph—* H
Compound 804 S S
Figure US10497881-20191203-C00767
 		H p-C8H17—Ph—* H
Compound 805 S S
Figure US10497881-20191203-C00768
 		H p-C9H19—Ph—* H
Compound 806 S S
Figure US10497881-20191203-C00769
 		H p-C10H21—Ph—* H
Compound 807 S S
Figure US10497881-20191203-C00770
 		H p-C11H23—Ph—* H
TABLE 31
Xb1 Xb2 Rb11 Rb12 Rb21 Rb22
Compound 808 S S
Figure US10497881-20191203-C00771
 		H p-C12H25—Ph—* H
Compound 809 S S
Figure US10497881-20191203-C00772
 		H p-C13H27—Ph—* H
Compound 810 S S
Figure US10497881-20191203-C00773
 		H p-C14H29—Ph—* H
Compound 811 S S
Figure US10497881-20191203-C00774
 		H p-C15H31—Ph—* H
Compound 812 S S
Figure US10497881-20191203-C00775
 		H p-C16H33—Ph—* H
Compound 813 S S
Figure US10497881-20191203-C00776
 		H p-C17H35—Ph—* H
Compound 814 S S
Figure US10497881-20191203-C00777
 		H p-C18H37—Ph—* H
Compound 815 S S H H H p-C5H11—Ph—*
Compound 816 S S H H H p-C6H13—Ph—*
Compound 817 S S H H H p-C7H15—Ph—*
Compound 818 S S H H H p-C8H17—Ph—*
Compound 819 S S H H H p-C9H19—Ph—*
Compound 820 S S H H H p-C10H21—Ph—*
Compound 821 S S H H H p-C11H23—Ph—*
Compound 822 S S H H H p-C12H25—Ph—*
Compound 823 S S H H H p-C13H27—Ph—*
Compound 824 S S H H H p-C14H29—Ph—*
Compound 825 S S H H H p-C15H31—Ph—*
Compound 826 S S H H H p-C16H33—Ph—*
Compound 827 S S H H H p-C17H35—Ph—*
Compound 828 S S H H H p-C18H37—Ph—*
Compound 829 S S H H
Figure US10497881-20191203-C00778
 		H
Compound 830 S S H H
Figure US10497881-20191203-C00779
 		H
Compound 831 S S H H
Figure US10497881-20191203-C00780
 		H
Compound 832 S S H H
Figure US10497881-20191203-C00781
 		H
Compound 833 S S H H
Figure US10497881-20191203-C00782
 		H
Compound 834 S S H H
Figure US10497881-20191203-C00783
 		H
TABLE 32
Xb1 Xb2 Rb11 Rb12 Rb21 Rb22
Compound 835 S S H H
Figure US10497881-20191203-C00784
 		H
Compound 836 S S H H
Figure US10497881-20191203-C00785
 		H
Compound 837 S S H H
Figure US10497881-20191203-C00786
 		H
Compound 838 S S H H
Figure US10497881-20191203-C00787
 		H
Compound 839 S S H H
Figure US10497881-20191203-C00788
 		H
Compound 840 S S H H
Figure US10497881-20191203-C00789
 		H
Compound 841 S S H H
Figure US10497881-20191203-C00790
 		H
Compound 842 S S Ph H
Figure US10497881-20191203-C00791
 		H
Compound 843 S S Ph H
Figure US10497881-20191203-C00792
 		H
Compound 844 S S Ph H
Figure US10497881-20191203-C00793
 		H
Compound 845 S S Ph H
Figure US10497881-20191203-C00794
 		H
Compound 846 S S Ph H
Figure US10497881-20191203-C00795
 		H
Compound 847 S S Ph H
Figure US10497881-20191203-C00796
 		H
Compound 848 S S Ph H
Figure US10497881-20191203-C00797
 		H
Compound 849 S S Ph H
Figure US10497881-20191203-C00798
 		H
Compound 850 S S Ph H
Figure US10497881-20191203-C00799
 		H
Compound 851 S S Ph H
Figure US10497881-20191203-C00800
 		H
Compound 852 S S Ph H
Figure US10497881-20191203-C00801
 		H
TABLE 33
Xb1 Xb2 Rb11 Rb12 Rb21 Rb22
Compound 853 S S Ph H
Figure US10497881-20191203-C00802
 		H
Compound 854 S S Ph H
Figure US10497881-20191203-C00803
 		H
Compound 855 S S
Figure US10497881-20191203-C00804
 		H
Figure US10497881-20191203-C00805
 		H
Compound 856 S S
Figure US10497881-20191203-C00806
 		H
Figure US10497881-20191203-C00807
 		H
Compound 857 S S
Figure US10497881-20191203-C00808
 		H
Figure US10497881-20191203-C00809
 		H
Compound 858 S S
Figure US10497881-20191203-C00810
 		H
Figure US10497881-20191203-C00811
 		H
Compound 859 S S
Figure US10497881-20191203-C00812
 		H
Figure US10497881-20191203-C00813
 		H
Compound 860 S S
Figure US10497881-20191203-C00814
 		H
Figure US10497881-20191203-C00815
 		H
Compound 861 S S
Figure US10497881-20191203-C00816
 		H
Figure US10497881-20191203-C00817
 		H
Compound 862 S S
Figure US10497881-20191203-C00818
 		H
Figure US10497881-20191203-C00819
 		H
Compound 863 S S
Figure US10497881-20191203-C00820
 		H
Figure US10497881-20191203-C00821
 		H
Compound 864 S S
Figure US10497881-20191203-C00822
 		H
Figure US10497881-20191203-C00823
 		H
Compound 865 S S
Figure US10497881-20191203-C00824
 		H
Figure US10497881-20191203-C00825
 		H
Compound 866 S S
Figure US10497881-20191203-C00826
 		H
Figure US10497881-20191203-C00827
 		H
Compound 867 S S
Figure US10497881-20191203-C00828
 		H
Figure US10497881-20191203-C00829
 		H
Compound 868 S S H H H
Figure US10497881-20191203-C00830
Compound 869 S S H H H
Figure US10497881-20191203-C00831
Compound 870 S S H H H
Figure US10497881-20191203-C00832
TABLE 34
Xb1 Xb2 Rb11 Rb12 Rb21 Rb22
Compound 871 S S H H H
Figure US10497881-20191203-C00833
Compound 872 S S H H H
Figure US10497881-20191203-C00834
Compound 873 S S H H H
Figure US10497881-20191203-C00835
Compound 874 S S H H H
Figure US10497881-20191203-C00836
Compound 875 S S H H H
Figure US10497881-20191203-C00837
Compound 876 S S H H H
Figure US10497881-20191203-C00838
Compound 877 S S H H H
Figure US10497881-20191203-C00839
Compound 878 S S H H H
Figure US10497881-20191203-C00840
Compound 879 S S H H H
Figure US10497881-20191203-C00841
Compound 880 S S H H H
Figure US10497881-20191203-C00842
Compound 881 S S H H
Figure US10497881-20191203-C00843
 		H
Compound 882 S S H H
Figure US10497881-20191203-C00844
 		H
Compound 883 S S H H
Figure US10497881-20191203-C00845
 		H
Compound 884 S S H H
Figure US10497881-20191203-C00846
 		H
Compound 885 S S H H
Figure US10497881-20191203-C00847
 		H
Compound 886 S S H H
Figure US10497881-20191203-C00848
 		H
Compound 887 S S H H
Figure US10497881-20191203-C00849
 		H
Compound 888 S S H H
Figure US10497881-20191203-C00850
 		H
TABLE 35
Xb1 Xb2 Rb11 Rb12 Rb21 Rb22
Compound 889 S S H H
Figure US10497881-20191203-C00851
 		H
Compound 890 S S H H
Figure US10497881-20191203-C00852
 		H
Compound 891 S S H H
Figure US10497881-20191203-C00853
 		H
Compound 892 S S H H
Figure US10497881-20191203-C00854
 		H
Compound 893 S S H H
Figure US10497881-20191203-C00855
 		H
Compound 894 S S H H
Figure US10497881-20191203-C00856
 		H
Compound 895 S S Ph H
Figure US10497881-20191203-C00857
 		H
Compound 896 S S Ph H
Figure US10497881-20191203-C00858
 		H
Compound 897 S S Ph H
Figure US10497881-20191203-C00859
 		H
Compound 898 S S Ph H
Figure US10497881-20191203-C00860
 		H
Compound 899 S S Ph H
Figure US10497881-20191203-C00861
 		H
Compound 900 S S Ph H
Figure US10497881-20191203-C00862
 		H
Compound 901 S S Ph H
Figure US10497881-20191203-C00863
 		H
Compound 902 S S Ph H
Figure US10497881-20191203-C00864
 		H
Compound 903 S S Ph H
Figure US10497881-20191203-C00865
 		H
Compound 904 S S Ph H
Figure US10497881-20191203-C00866
 		H
Compound 905 S S Ph H
Figure US10497881-20191203-C00867
 		H
Compound 906 S S Ph H
Figure US10497881-20191203-C00868
 		H
TABLE 36
Xb1 Xb2 Rb11 Rb12 Rb21 Rb22
Compound 907 S S Ph H
Figure US10497881-20191203-C00869
 		H
Compound 908 S S Ph H
Figure US10497881-20191203-C00870
 		H
Compound 909 S S
Figure US10497881-20191203-C00871
 		H
Figure US10497881-20191203-C00872
 		H
Compound 910 S S
Figure US10497881-20191203-C00873
 		H
Figure US10497881-20191203-C00874
 		H
Compound 911 S S
Figure US10497881-20191203-C00875
 		H
Figure US10497881-20191203-C00876
 		H
Compound 912 S S
Figure US10497881-20191203-C00877
 		H
Figure US10497881-20191203-C00878
 		H
Compound 913 S S
Figure US10497881-20191203-C00879
 		H
Figure US10497881-20191203-C00880
 		H
Compound 914 S S
Figure US10497881-20191203-C00881
 		H
Figure US10497881-20191203-C00882
 		H
Compound 915 S S
Figure US10497881-20191203-C00883
 		H
Figure US10497881-20191203-C00884
 		H
Compound 916 S S
Figure US10497881-20191203-C00885
 		H
Figure US10497881-20191203-C00886
 		H
Compound 917 S S
Figure US10497881-20191203-C00887
 		H
Figure US10497881-20191203-C00888
 		H
Compound 918 S S
Figure US10497881-20191203-C00889
 		H
Figure US10497881-20191203-C00890
 		H
Compound 919 S S
Figure US10497881-20191203-C00891
 		H
Figure US10497881-20191203-C00892
 		H
Compound 920 S S
Figure US10497881-20191203-C00893
 		H
Figure US10497881-20191203-C00894
 		H
Compound 921 S S
Figure US10497881-20191203-C00895
 		H
Figure US10497881-20191203-C00896
 		H
Compound 922 S S
Figure US10497881-20191203-C00897
 		H
Figure US10497881-20191203-C00898
 		H
Compound 923 S S C10H21—* H p-C5H11—Ph—* H
Compound 924 S S C10H21—* H p-C6H13—Ph—* H
Compound 925 S S C10H21—* H p-C7H15—Ph—* H
Compound 926 S S C10H21—* H p-C8H17—Ph—* H
Compound 927 S S C10H21—* H p-C9H19—Ph—* H
Compound 928 S S C10H21—* H p-C10H21—Ph—* H
Compound 929 S S C10H21—* H p-C11H23—Ph—* H
Compound 930 S S C10H21—* H p-C12H25—Ph—* H
TABLE 37 Xb1 Xb2 Rb11 Rb12 Rb21 Rb22
Compound S S C10H21—* H p-C13H27—Ph—* H
931
Compound S S C10H21—* H p-C14H29—Ph—* H
932
Compound S S C10H21—* H p-C15H31—Ph—* H
933
Compound S S C10H21—* H p-C16H33—Ph—* H
934
Compound S S C10H21—* H p-C17H35—Ph—* H
935
Compound S S C10H21—* H p-C18H37—Ph—* H
936
Compound 937 S S C12H25—* H
Figure US10497881-20191203-C00899
 		H
Compound 938 S S C12H25—* H
Figure US10497881-20191203-C00900
 		H
Compound 939 S S C12H25—* H
Figure US10497881-20191203-C00901
 		H
Compound 940 S S C12H25—* H
Figure US10497881-20191203-C00902
 		H
Compound 941 S S C12H25—* H
Figure US10497881-20191203-C00903
 		H
Compound 942 S S C12H25—* H
Figure US10497881-20191203-C00904
 		H
Compound 943 S S C12H25—* H
Figure US10497881-20191203-C00905
 		H
Compound 944 S S C12H25—* H
Figure US10497881-20191203-C00906
 		H
Compound 945 S S C12H25-* H
Figure US10497881-20191203-C00907
 		H
Compound 946 S S C12H25—* H
Figure US10497881-20191203-C00908
 		H
Compound 947 S S C12H25—* H
Figure US10497881-20191203-C00909
 		H
Compound 948 S S C12H25—* H
Figure US10497881-20191203-C00910
 		H
Compound 949 S S C12H25—* H
Figure US10497881-20191203-C00911
 		H
Compound 950 S S C12H25—* H
Figure US10497881-20191203-C00912
 		H
Compound S S C5H11—* H H C12H25—*
951
Compound S S C6H13—* H H C12H25—*
952
Compound S S C7H15—* H H C12H25—*
953
Compound S S C8H17—* H H C12H25—*
954
Compound S S C9H19—* H H C12H25—*
955
Compound S S C10H21—* H H C12H25—*
956
Compound S S C11H23—* H H C12H25—*
957
Compound S S C12H25—* H H C12H25—*
958
TABLE 38
Xb1 Xb2 Rb11 Rb12 Rb21 Rb22
Compound 959 S S C13H27—* H H C12H25—*
Compound 960 S S C14H29—* H H C12H25—*
Compound 961 S S C15H31—* H H C12H25—*
Compound 962 S S C16H33—* H H C12H25—*
Compound 963 S S C17H35—* H H C12H25—*
Compound 964 S S C18H37—* H H C12H25—*
Compound 965 S S C10H21—* H H p-C5H11—Ph—*
Compound 966 S S C10H21—* H H p-C6H13—Ph—*
Compound 967 S S C10H21—* H H p-C7H15—Ph—*
Compound 968 S S C10H21—* H H p-C8H17—Ph—*
Compound 969 S S C10H21—* H H p-C9H19—Ph—*
Compound 970 S S C10H21—* H H p-C10H21—Ph—*
Compound 971 S S C10H21—* H H p-C11H23—Ph—*
Compound 972 S S C10H21—* H H p-C12H25—Ph—*
Compound 973 S S C10H21—* H H p-C13H27—Ph—*
Compound 974 S S C10H21—* H H p-C14H29—Ph—*
Compound 975 S S C10H21—* H H p-C15H31—Ph—*
Compound 976 S S C10H21—* H H p-C16H33—Ph—*
Compound 977 S S C10H21—* H H p-C17H35—Ph—*
Compound 978 S S C10H21—* H H p-C18H37—Ph—*
Compound 979 S S H C10H21—* H p-C5H11—Ph—*
Compound 980 S S H C10H21—* H p-C6H13—Ph—*
Compound 981 S S H C10H21—* H p-C7H15—Ph—*
Compound 982 S S H C10H21—* H p-C8H17—Ph—*
Compound 983 S S H C10H21—* H p-C9H19—Ph—*
Compound 984 S S H C10H21—* H p-C10H21—Ph—*
Compound 985 S S H C10H21—* H p-C11H23—Ph—*
Compound 986 S S H C10H21—* H p-C12H25—Ph—*
Compound 987 S S H C10H21—* H p-C13H27—Ph—*
Compound 988 S S H C10H21—* H p-C14H29—Ph—*
Compound 989 S S H C10H21—* H p-C15H31—Ph—*
Compound 990 S S H C10H21—* H p-C16H33—Ph—*
Compound 991 S S H C10H21—* H p-C17H35—Ph—*
Compound 992 S S H C10H21—* H p-C18H37—Ph—*
Compound 993 S S
Figure US10497881-20191203-C00913
 		H
Figure US10497881-20191203-C00914
 		H
Compound 994 S S
Figure US10497881-20191203-C00915
 		H
Figure US10497881-20191203-C00916
 		H
Compound 995 S S
Figure US10497881-20191203-C00917
 		H
Figure US10497881-20191203-C00918
 		H
Compound 996 S S
Figure US10497881-20191203-C00919
 		H
Figure US10497881-20191203-C00920
 		H
Compound 997 S S
Figure US10497881-20191203-C00921
 		H
Figure US10497881-20191203-C00922
 		H
Compound 998 S S
Figure US10497881-20191203-C00923
 		H
Figure US10497881-20191203-C00924
 		H
TABLE 39
Xb1 Xb2 Rb11 Rb12 Rb21 Rb22
Compound 999  S S
Figure US10497881-20191203-C00925
 		H
Figure US10497881-20191203-C00926
 		H
Compound 1000 S S
Figure US10497881-20191203-C00927
 		H
Figure US10497881-20191203-C00928
 		H
Compound 1001 S S
Figure US10497881-20191203-C00929
 		H
Figure US10497881-20191203-C00930
 		H
Compound 1002 S S
Figure US10497881-20191203-C00931
 		H
Figure US10497881-20191203-C00932
 		H
Compound 1003 S S
Figure US10497881-20191203-C00933
 		H
Figure US10497881-20191203-C00934
 		H
Compound 1004 S S
Figure US10497881-20191203-C00935
 		H
Figure US10497881-20191203-C00936
 		H
Compound 1005 S S
Figure US10497881-20191203-C00937
 		H
Figure US10497881-20191203-C00938
 		H
Compound 1006 S S
Figure US10497881-20191203-C00939
 		H
Figure US10497881-20191203-C00940
 		H
Compound 1007 S S
Figure US10497881-20191203-C00941
 		H
Figure US10497881-20191203-C00942
 		H
Compound 1008 S S
Figure US10497881-20191203-C00943
 		H
Figure US10497881-20191203-C00944
 		H
Compound 1009 S S
Figure US10497881-20191203-C00945
 		H
Figure US10497881-20191203-C00946
 		H
Compound 1010 S S
Figure US10497881-20191203-C00947
 		H
Figure US10497881-20191203-C00948
 		H
Compound 1011 S S
Figure US10497881-20191203-C00949
 		H
Figure US10497881-20191203-C00950
 		H
Compound 1012 S S
Figure US10497881-20191203-C00951
 		H
Figure US10497881-20191203-C00952
 		H
Compound 1013 S S
Figure US10497881-20191203-C00953
 		H
Figure US10497881-20191203-C00954
 		H
Compound 1014 S S
Figure US10497881-20191203-C00955
 		H
Figure US10497881-20191203-C00956
 		H
Compound 1015 S S
Figure US10497881-20191203-C00957
 		H
Figure US10497881-20191203-C00958
 		H
Compound 1016 S S
Figure US10497881-20191203-C00959
 		H
Figure US10497881-20191203-C00960
 		H
TABLE 40
Xb1 Xb2 Rb11 Rb12 Rb21 Rb22
Compound 1017 S S
Figure US10497881-20191203-C00961
 		H
Figure US10497881-20191203-C00962
 		H
Compound 1018 S S
Figure US10497881-20191203-C00963
 		H
Figure US10497881-20191203-C00964
 		H
Compound 1019 S S
Figure US10497881-20191203-C00965
 		H
Figure US10497881-20191203-C00966
 		H
Compound 1020 S S
Figure US10497881-20191203-C00967
 		H
Figure US10497881-20191203-C00968
 		H
Compound 1021 S S
Figure US10497881-20191203-C00969
 		H
Figure US10497881-20191203-C00970
 		H
Compound 1022 S S
Figure US10497881-20191203-C00971
 		H
Figure US10497881-20191203-C00972
 		H
Compound 1023 S S
Figure US10497881-20191203-C00973
 		H
Figure US10497881-20191203-C00974
 		H
Compound 1024 S S
Figure US10497881-20191203-C00975
 		H
Figure US10497881-20191203-C00976
 		H
Compound 1025 S S
Figure US10497881-20191203-C00977
 		H
Figure US10497881-20191203-C00978
 		H
Compound 1026 S S
Figure US10497881-20191203-C00979
 		H
Figure US10497881-20191203-C00980
 		H
Compound 1027 S S
Figure US10497881-20191203-C00981
 		H
Figure US10497881-20191203-C00982
 		H
Compound 1028 S S
Figure US10497881-20191203-C00983
 		H
Figure US10497881-20191203-C00984
 		H
Compound 1029 S S
Figure US10497881-20191203-C00985
 		H
Figure US10497881-20191203-C00986
 		H
Compound 1030 S S
Figure US10497881-20191203-C00987
 		H
Figure US10497881-20191203-C00988
 		H
Compound 1031 S S
Figure US10497881-20191203-C00989
 		H
Figure US10497881-20191203-C00990
 		H
Compound 1032 S S
Figure US10497881-20191203-C00991
 		H
Figure US10497881-20191203-C00992
 		H
Compound 1033 S S
Figure US10497881-20191203-C00993
 		H
Figure US10497881-20191203-C00994
 		H
Compound 1034 O O C5H11—* H C5H11—* H
Compound 1035 O O C6H13—* H C6H13—* H
Compound 1036 O O C7H15—* H C7H15—* H
Compound 1037 O O C8H17—* H C8H17—* H
Compound 1038 O O C9H19—* H C9H19—* H
TABLE 41
Xb1 Xb2 Rb11 Rb12 Rb21 Rb22
Compound 1039 O O C10H21—* H C10H21—* H
Compound 1040 O O C11H23—* H C11H23—* H
Compound 1041 O O C12H25—* H C12H25—* H
Compound 1042 O O C13H27—* H C13H27—* H
Compound 1043 O O C14H29—* H C14H29—* H
Compound 1044 O O C15H31—* H C15H31—* H
Compound 1045 O O C16H33—* H C16H33—* H
Compound 1046 O O C17H35—* H C17H35—* H
Compound 1047 O O C18H37—* H C18H37—* H
Compound 1048 O O p-C5H11—Ph—* H p-C5H11—Ph—* H
Compound 1049 O O p-C6H13—Ph—* H p-C6H13—Ph—* H
Compound 1050 O O p-C7H15—Ph—* H p-C7H15—Ph—* H
Compound 1051 O O p-C8H17—Ph—* H p-C8H17—Ph—* H
Compound 1052 O O p-C9H19—Ph—* H p-C9H19—Ph—* H
Compound 1053 O O p-C10H21—Ph—* H p-C10H21—Ph—* H
Compound 1054 O O p-C11H23—Ph—* H p-C11H23—Ph—* H
Compound 1055 O O p-C12H25—Ph—* H p-C12H25—Ph—* H
Compound 1056 O O p-C13H27—Ph—* H p-C13H27—Ph—* H
Compound 1057 O O p-C14H29—Ph—* H p-C14H29—Ph—* H
Compound 1058 O O p-C15H31—Ph—* H p-C15H31—Ph—* H
Compound 1059 O O p-C16H33—Ph—* H p-C16H33—Ph—* H
Compound 1060 O O p-C17H35—Ph—* H p-C17H35—Ph—* H
Compound 1061 O O p-C18H37—Ph—* H p-C18H37—Ph—* H
Compound 1062 O O
Figure US10497881-20191203-C00995
 		H
Figure US10497881-20191203-C00996
 		H
Compound 1063 O O
Figure US10497881-20191203-C00997
 		H
Figure US10497881-20191203-C00998
 		H
Compound 1064 O O
Figure US10497881-20191203-C00999
 		H
Figure US10497881-20191203-C01000
 		H
Compound 1065 O O
Figure US10497881-20191203-C01001
 		H
Figure US10497881-20191203-C01002
 		H
Compound 1066 O O
Figure US10497881-20191203-C01003
 		H
Figure US10497881-20191203-C01004
 		H
Compound 1067 O O
Figure US10497881-20191203-C01005
 		H
Figure US10497881-20191203-C01006
 		H
Compound 1068 O O
Figure US10497881-20191203-C01007
 		H
Figure US10497881-20191203-C01008
 		H
Compound 1069 O O
Figure US10497881-20191203-C01009
 		H
Figure US10497881-20191203-C01010
 		H
Compound 1070 O O
Figure US10497881-20191203-C01011
 		H
Figure US10497881-20191203-C01012
 		H
Compound 1071 O O
Figure US10497881-20191203-C01013
 		H
Figure US10497881-20191203-C01014
 		H
TABLE 42
Xb1 Xb2 Rb11 Rb12 Rb21 Rb22
Compound 1072 O O
Figure US10497881-20191203-C01015
 		H
Figure US10497881-20191203-C01016
 		H
Compound 1073 O O
Figure US10497881-20191203-C01017
 		H
Figure US10497881-20191203-C01018
 		H
Compound 1074 O O
Figure US10497881-20191203-C01019
 		H
Figure US10497881-20191203-C01020
 		H
Compound 1075 O O
Figure US10497881-20191203-C01021
 		H
Figure US10497881-20191203-C01022
 		H
Compound 1076 S S C4H3OC4H8—* H C4H3OC4H8—* H
Compound 1077 S S C2H5OC2H4—* H C2H5OC2H4—* H
Compound 1078 S S C6H13OC4H8—* H C6H13OC4H8—* H
Compound 1079 S S C2H5OC4H8—* H C2H5OC4H8—* H
Compound 1080 S S CH3OC3H5—* H CH3OC3H5—* H
Compound 1081 S S
Figure US10497881-20191203-C01023
 		H
Figure US10497881-20191203-C01024
 		H
Compound 1082 S S
Figure US10497881-20191203-C01025
 		H
Figure US10497881-20191203-C01026
 		H
Compound 1083 S S
Figure US10497881-20191203-C01027
 		H
Figure US10497881-20191203-C01028
 		H
Compound 1084 S S PhO3H6—* H PhO3H6—* H
Compound 1085 S S PhOC3H6—* H PhOC3H6—* H
Compound 1086 S S
Figure US10497881-20191203-C01029
 		H
Figure US10497881-20191203-C01030
 		H
Compound 1087 S S
Figure US10497881-20191203-C01031
 		H
Figure US10497881-20191203-C01032
 		H
Compound 1088 S S
Figure US10497881-20191203-C01033
 		H
Figure US10497881-20191203-C01034
 		H
Compound 1089 S S
Figure US10497881-20191203-C01035
 		H
Figure US10497881-20191203-C01036
 		H
Compound 1090 S S
Figure US10497881-20191203-C01037
 		H
Figure US10497881-20191203-C01038
 		H
Compound 1091 S S 3,7-Dimethyloctyl H 3,7-Dimethyloctyl H
Compound 1092 S S 3,7-Dimethyloctyl H H H
Compound 1093 S S 2-Ethylhexyl H 2-Ethylhexyl H
Compound 1094 S S
Figure US10497881-20191203-C01039
 		H
Figure US10497881-20191203-C01040
 		H
Compound 1095 S S
Figure US10497881-20191203-C01041
 		H
Figure US10497881-20191203-C01042
 		H
TABLE 43
Xb1 Xb2 Rb11 Rb12 Rb21 Rb22
Compound 1096 S S
Figure US10497881-20191203-C01043
 		H
Figure US10497881-20191203-C01044
 		H
Compound 1097 S S
Figure US10497881-20191203-C01045
 		H H H
Compound 1098 S S
Figure US10497881-20191203-C01046
 		H
Figure US10497881-20191203-C01047
 		H
Compound 1099 S S C5H11—* H
Figure US10497881-20191203-C01048
 		H
Compound 1100 S S
Figure US10497881-20191203-C01049
 		H
Figure US10497881-20191203-C01050
 		H
Compound 1101 S S
Figure US10497881-20191203-C01051
 		H
Figure US10497881-20191203-C01052
 		H
Compound 1102 S S
Figure US10497881-20191203-C01053
 		H
Figure US10497881-20191203-C01054
 		H
Compound 1103 S S
Figure US10497881-20191203-C01055
 		H
Figure US10497881-20191203-C01056
 		H
Compound 1104 S S
Figure US10497881-20191203-C01057
 		H
Figure US10497881-20191203-C01058
 		H
Compound 1105 S S
Figure US10497881-20191203-C01059
 		H H H
Compound 1106 S S
Figure US10497881-20191203-C01060
 		H
Figure US10497881-20191203-C01061
 		H
Compound 1107 S S
Figure US10497881-20191203-C01062
 		H
Figure US10497881-20191203-C01063
 		H
Compound 1108 S S
Figure US10497881-20191203-C01064
 		H
Figure US10497881-20191203-C01065
 		H
Compound 1109 S S
Figure US10497881-20191203-C01066
 		H
Figure US10497881-20191203-C01067
 		H
TABLE 44
Xc1 Xc2 Rc11 Rc21
Compound S S C5H11—* C5H11—*
1110
Compound S S C6H13—* C6H13—*
1111
Compound S S C7H15—* C7H15—*
1112
Compound S S C8H17—* C8H17—*
1113
Compound S S C9H19—* C9H19—*
1114
Compound S S C10H21—* C10H21—*
1115
Compound S S C11H23—* C11H23—*
1116
Compound S S C12H25—* C12H25—*
1117
Compound S S C13H27—* C13H27—*
1118
Compound S S C14H29—* C14H29—*
1119
Compound S S C15H31—* C15H31—*
1120
Compound S S C16H33—* C16H33—*
1121
Compound S S C17H35—* C17H35—*
1122
Compound S S C18H37—* C18H37—*
1123
Compound S S p-C5H11—Ph—* p-C5H11—Ph—*
1124
Compound S S p-C6H13—Ph—* p-C6H13—Ph—*
1125
Compound S S p-C7H15—Ph—* p-C7H15—Ph—*
1126
Compound S S p-C8H17—Ph—* p-C8H17—Ph—*
1127
Compound S S p-C9H19—Ph—* p-C9H19—Ph—*
1128
Compound S S p-C10H21—Ph—* p-C10H21—Ph—*
1129
Compound S S p-C11H23—Ph—* p-C11H23—Ph—*
1130
Compound S S p-C12H25—Ph—* p-C12H25—Ph—*
1131
Compound S S p-C13H27—Ph—* p-C13H27—Ph—*
1132
Compound S S p-C14H29—Ph—* p-C14H29—Ph—*
1133
Compound S S p-C15H31—Ph—* p-C15H31—Ph—*
1134
Compound S S p-C16H33—Ph—* p-C16H33—Ph—*
1135
Compound S S p-C17H35—Ph—* p-C17H35—Ph—*
1136
Compound S S p-C18H37—Ph—* p-C18H37—Ph—*
1137
Compound 1138 S S
Figure US10497881-20191203-C01068
Figure US10497881-20191203-C01069
Compound 1139 S S
Figure US10497881-20191203-C01070
Figure US10497881-20191203-C01071
Compound 1140 S S
Figure US10497881-20191203-C01072
Figure US10497881-20191203-C01073
Compound 1141 S S
Figure US10497881-20191203-C01074
Figure US10497881-20191203-C01075
Compound 1142 S S
Figure US10497881-20191203-C01076
Figure US10497881-20191203-C01077
Compound 1143 S S
Figure US10497881-20191203-C01078
Figure US10497881-20191203-C01079
Compound 1144 S S
Figure US10497881-20191203-C01080
Figure US10497881-20191203-C01081
Compound 1145 S S
Figure US10497881-20191203-C01082
Figure US10497881-20191203-C01083
TABLE 45
xc1 Xc2 Rc11 Rc21
Com- pound 1146 S S
Figure US10497881-20191203-C01084
Figure US10497881-20191203-C01085
Com- pound 1147 S S
Figure US10497881-20191203-C01086
Figure US10497881-20191203-C01087
Com- pound 1148 S S
Figure US10497881-20191203-C01088
Figure US10497881-20191203-C01089
Com- pound 1149 S S
Figure US10497881-20191203-C01090
Figure US10497881-20191203-C01091
Com- pound 1150 S S
Figure US10497881-20191203-C01092
Figure US10497881-20191203-C01093
Com- pound 1151 S S
Figure US10497881-20191203-C01094
Figure US10497881-20191203-C01095
Com- pound 1152 S S
Figure US10497881-20191203-C01096
Figure US10497881-20191203-C01097
Com- pound 1153 S S
Figure US10497881-20191203-C01098
Figure US10497881-20191203-C01099
Com- pound 1154 S S
Figure US10497881-20191203-C01100
Figure US10497881-20191203-C01101
Com- pound 1155 S S
Figure US10497881-20191203-C01102
Figure US10497881-20191203-C01103
Com- pound 1156 S S
Figure US10497881-20191203-C01104
Figure US10497881-20191203-C01105
Com- pound 1157 S S
Figure US10497881-20191203-C01106
Figure US10497881-20191203-C01107
Com- pound 1158 S S
Figure US10497881-20191203-C01108
Figure US10497881-20191203-C01109
Com- pound 1159 S S
Figure US10497881-20191203-C01110
Figure US10497881-20191203-C01111
Com- pound 1160 S S
Figure US10497881-20191203-C01112
Figure US10497881-20191203-C01113
Com- pound 1161 S S
Figure US10497881-20191203-C01114
Figure US10497881-20191203-C01115
Com- pound 1162 S S
Figure US10497881-20191203-C01116
Figure US10497881-20191203-C01117
Com- pound 1163 S S
Figure US10497881-20191203-C01118
Figure US10497881-20191203-C01119
TABLE 46
Xc1 Xc2 Rc11 Rc21
Com- pound 1164 S S
Figure US10497881-20191203-C01120
Figure US10497881-20191203-C01121
Com- pound 1165 S S
Figure US10497881-20191203-C01122
Figure US10497881-20191203-C01123
Com- S S H C5H11—*
pound
1166
Com- S S H C6H13—*
pound
1167
Com- S S H C7H15—*
pound
1168
Com- S S H C8H17—*
pound
1169
Com- S S H C9H19—*
pound
1170
Com- S S H C10H21—*
pound
1171
Com- S S H C11H23—*
pound
1172
Com- S S H C12H25—*
pound
1173
Com- S S H C13H27—*
pound
1174
Com- S S H C14H29—*
pound
1175
Com- S S H C15H31—*
pound
1176
Com- S S H C16H33—*
pound
1177
Com- S S H C17H35—*
pound
1178
Com- S S H C18H37—*
pound
1179
Com- S S Ph C5H11—*
pound
1180
Com- S S Ph C6H13—*
pound
1181
Com- S S Ph C7H15—*
pound
1182
Com- S S Ph C8H17—*
pound
1183
Com- S S Ph C9H19—*
pound
1184
Com- S S Ph C10H21—*
pound
1185
Com- S S Ph C11H23—*
pound
1186
Com- S S Ph C12H25—*
pound
1187
Com- S S Ph C13H27—*
pound
1188
Com- S S Ph C14H29—*
pound
1189
Com- S S Ph C15H31—*
pound
1190
Com- S S Ph C16H33—*
pound
1191
Com- S S Ph C17H35—*
pound
1192
Com- S S Ph C18H37—*
pound
1193
Com- pound 1194 S S
Figure US10497881-20191203-C01124
 		C5H11—*
Com- pound 1195 S S
Figure US10497881-20191203-C01125
 		C6H13—*
Com- pound 1196 S S
Figure US10497881-20191203-C01126
 		C7H15—*
Com- pound 1197 S S
Figure US10497881-20191203-C01127
 		C8H17—*
Com- pound 1198 S S
Figure US10497881-20191203-C01128
 		C9H19—*
Com- pound 1199 S S
Figure US10497881-20191203-C01129
 		C10C21—*
TABLE 47
Xc1 Xc2 Rc11 Rc21
Compound 1200 S S
Figure US10497881-20191203-C01130
 		C11C23—*
Compound 1201 S S
Figure US10497881-20191203-C01131
 		C12C25—*
Compound 1202 S S
Figure US10497881-20191203-C01132
 		C13C27—*
Compound 1203 S S
Figure US10497881-20191203-C01133
 		C14C29—*
Compound 1204 S S
Figure US10497881-20191203-C01134
 		C15C31—*
Compound 1205 S S
Figure US10497881-20191203-C01135
 		C16C33—*
Compound 1206 S S
Figure US10497881-20191203-C01136
 		C17C35—*
Compound 1207 S S
Figure US10497881-20191203-C01137
 		C18C37—*
Compound 1208 S S H p-C5H11—Ph—*
Compound 1209 S S H p-C6H13—Ph—*
Compound 1210 S S H p-C7H15—Ph—*
Compound 1211 S S H p-C8H17—Ph—*
Compound 1212 S S H p-C9H19—Ph—*
Compound 1213 S S H p-C10H21—Ph—*
Compound 1214 S S H p-C11H23—Ph—*
Compound 1215 S S H p-C12H25—Ph—*
Compound 1216 S S H p-C13H27—Ph—*
Compound 1217 S S H p-C14H29—Ph—*
Compound 1218 S S H p-C15H31—Ph—*
Compound 1219 S S H p-C16H33—Ph—*
Compound 1220 S S H p-C17H35—Ph—*
Compound 1221 S S H p-C18H37—Ph—*
Compound 1222 S S Ph p-C5H11—Ph—*
Compound 1223 S S Ph p-C6H13—Ph—*
Compound 1224 S S Ph p-C7H15—Ph—*
Compound 1225 S S Ph p-C8H17—Ph—*
Compound 1226 S S Ph p-C9H19—Ph—*
Compound 1227 S S Ph p-C10H21—Ph—*
Compound 1228 S S Ph p-C11H23—Ph—*
Compound 1229 S S Ph p-C12H25—Ph—*
Compound 1230 S S Ph p-C13H27—Ph—*
Compound 1231 S S Ph p-C14H29—Ph—*
Compound 1232 S S Ph p-C15H31—Ph—*
Compound 1233 S S Ph p-C16H33—Ph—*
Compound 1234 S S Ph p-C17H35—Ph—*
Compound 1235 S S Ph p-C18H37—Ph—*
TABLE 48
Xc1 Xc2 Rc11 Rc21
Compound 1236 S S
Figure US10497881-20191203-C01138
 		p-C5H11—Ph—*
Compound 1237 S S
Figure US10497881-20191203-C01139
 		p-C6H13—Ph—*
Compound 1238 S S
Figure US10497881-20191203-C01140
 		p-C7H15—Ph—*
Compound 1239 S S
Figure US10497881-20191203-C01141
 		p-C8H17—Ph—*
Compound 1240 S S
Figure US10497881-20191203-C01142
 		p-C9H19—Ph—*
Compound 1241 S S
Figure US10497881-20191203-C01143
 		p-C10H21—Ph—*
Compound 1242 S S
Figure US10497881-20191203-C01144
 		p-C11H23—Ph—*
Compound 1243 S S
Figure US10497881-20191203-C01145
 		p-C12H25—Ph—*
Compound 1244 S S
Figure US10497881-20191203-C01146
 		p-C13H27—Ph—*
Compound 1245 S S
Figure US10497881-20191203-C01147
 		p-C14H29—Ph—*
Compound 1246 S S
Figure US10497881-20191203-C01148
 		p-C15H31—Ph—*
Compound 1247 S S
Figure US10497881-20191203-C01149
 		p-C16H33—Ph—*
Compound 1248 S S
Figure US10497881-20191203-C01150
 		p-C17H35—Ph—*
Compound 1249 S S
Figure US10497881-20191203-C01151
 		p-C18H37—Ph—*
Compound 1250 S S H
Figure US10497881-20191203-C01152
Compound 1251 S S H
Figure US10497881-20191203-C01153
Compound 1252 S S H
Figure US10497881-20191203-C01154
Compound 1253 S S H
Figure US10497881-20191203-C01155
TABLE 49
Xc1 Xc2 Rc11 Rc21
Compound 1254 S S H
Figure US10497881-20191203-C01156
Compound 1255 S S H
Figure US10497881-20191203-C01157
Compound 1256 S S H
Figure US10497881-20191203-C01158
Compound 1257 S S H
Figure US10497881-20191203-C01159
Compound 1258 S S H
Figure US10497881-20191203-C01160
Compound 1259 S S H
Figure US10497881-20191203-C01161
Compound 1260 S S H
Figure US10497881-20191203-C01162
Compound 1261 S S H
Figure US10497881-20191203-C01163
Compound 1262 S S H
Figure US10497881-20191203-C01164
Compound 1263 S S Ph
Figure US10497881-20191203-C01165
Compound 1264 S S Ph
Figure US10497881-20191203-C01166
Compound 1265 S S Ph
Figure US10497881-20191203-C01167
Compound 1266 S S Ph
Figure US10497881-20191203-C01168
Compound 1267 S S Ph
Figure US10497881-20191203-C01169
Compound 1268 S S Ph
Figure US10497881-20191203-C01170
Compound 1269 S S Ph
Figure US10497881-20191203-C01171
Compound 1270 S S Ph
Figure US10497881-20191203-C01172
Compound 1271 S S Ph
Figure US10497881-20191203-C01173
TABLE 50
Xc1 Xc2 Rc11 Rc21
Com- pound 1272 S S Ph
Figure US10497881-20191203-C01174
Com- pound 1273 S S Ph
Figure US10497881-20191203-C01175
Com- pound 1274 S S Ph
Figure US10497881-20191203-C01176
Com- pound 1275 S S Ph
Figure US10497881-20191203-C01177
Com- pound 1276 S S
Figure US10497881-20191203-C01178
Figure US10497881-20191203-C01179
Com- pound 1277 S S
Figure US10497881-20191203-C01180
Figure US10497881-20191203-C01181
Com- pound 1278 S S
Figure US10497881-20191203-C01182
Figure US10497881-20191203-C01183
Com- pound 1279 S S
Figure US10497881-20191203-C01184
Figure US10497881-20191203-C01185
Com- pound 1280 S S
Figure US10497881-20191203-C01186
Figure US10497881-20191203-C01187
Com- pound 1281 S S
Figure US10497881-20191203-C01188
Figure US10497881-20191203-C01189
Com- pound 1282 S S
Figure US10497881-20191203-C01190
Figure US10497881-20191203-C01191
Com- pound 1283 S S
Figure US10497881-20191203-C01192
Figure US10497881-20191203-C01193
Com- pound 1284 S S
Figure US10497881-20191203-C01194
Figure US10497881-20191203-C01195
Com- pound 1285 S S
Figure US10497881-20191203-C01196
Figure US10497881-20191203-C01197
Com- pound 1286 S S
Figure US10497881-20191203-C01198
Figure US10497881-20191203-C01199
Com- pound 1287 S S
Figure US10497881-20191203-C01200
Figure US10497881-20191203-C01201
Com- pound 1288 S S
Figure US10497881-20191203-C01202
Figure US10497881-20191203-C01203
Com- pound 1289 S S H
Figure US10497881-20191203-C01204
TABLE 51
Xc1 Xc2 Rc11 Rc21
Compound 1290 S S H
Figure US10497881-20191203-C01205
Compound 1291 S S H
Figure US10497881-20191203-C01206
Compound 1292 S S H
Figure US10497881-20191203-C01207
Compound 1293 S S H
Figure US10497881-20191203-C01208
Compound 1294 S S H
Figure US10497881-20191203-C01209
Compound 1295 S S H
Figure US10497881-20191203-C01210
Compound 1296 S S H
Figure US10497881-20191203-C01211
Compound 1297 S S H
Figure US10497881-20191203-C01212
Compound 1298 S S H
Figure US10497881-20191203-C01213
Compound 1299 S S H
Figure US10497881-20191203-C01214
Compound 1300 S S H
Figure US10497881-20191203-C01215
Compound 1301 S S H
Figure US10497881-20191203-C01216
Compound 1302 S S H
Figure US10497881-20191203-C01217
Compound 1303 S S Ph
Figure US10497881-20191203-C01218
Compound 1304 S S Ph
Figure US10497881-20191203-C01219
Compound 1305 S S Ph
Figure US10497881-20191203-C01220
Compound 1306 S S Ph
Figure US10497881-20191203-C01221
Compound 1307 S S Ph
Figure US10497881-20191203-C01222
TABLE 52
Xc1 Xc2 Rc11 Rc21
Compound 1308 S S Ph
Figure US10497881-20191203-C01223
Compound 1309 S S Ph
Figure US10497881-20191203-C01224
Compound 1310 S S Ph
Figure US10497881-20191203-C01225
Compound 1311 S S Ph
Figure US10497881-20191203-C01226
Compound 1312 S S Ph
Figure US10497881-20191203-C01227
Compound 1313 S S Ph
Figure US10497881-20191203-C01228
Compound 1314 S S Ph
Figure US10497881-20191203-C01229
Compound 1315 S S Ph
Figure US10497881-20191203-C01230
Compound 1316 S S Ph
Figure US10497881-20191203-C01231
Compound 1317 S S
Figure US10497881-20191203-C01232
Figure US10497881-20191203-C01233
Compound 1318 S S
Figure US10497881-20191203-C01234
Figure US10497881-20191203-C01235
Compound 1319 S S
Figure US10497881-20191203-C01236
Figure US10497881-20191203-C01237
Compound 1320 S S
Figure US10497881-20191203-C01238
Figure US10497881-20191203-C01239
Compound 1321 S S
Figure US10497881-20191203-C01240
Figure US10497881-20191203-C01241
Compound 1322 S S
Figure US10497881-20191203-C01242
Figure US10497881-20191203-C01243
Compound 1323 S S
Figure US10497881-20191203-C01244
Figure US10497881-20191203-C01245
Compound 1324 S S
Figure US10497881-20191203-C01246
Figure US10497881-20191203-C01247
Compound 1325 S S
Figure US10497881-20191203-C01248
Figure US10497881-20191203-C01249
TABLE 53
Xc1 Xc2 Rc11 Rc21
Com- pound 1326 S S
Figure US10497881-20191203-C01250
Figure US10497881-20191203-C01251
Com- pound 1327 S S
Figure US10497881-20191203-C01252
Figure US10497881-20191203-C01253
Com- pound 1328 S S
Figure US10497881-20191203-C01254
Figure US10497881-20191203-C01255
Com- pound 1329 S S
Figure US10497881-20191203-C01256
Figure US10497881-20191203-C01257
Com- pound 1330 S S
Figure US10497881-20191203-C01258
Figure US10497881-20191203-C01259
Com- S S C10H21—* p-C5H11—Ph—*
pound
1331
Com- S S C10H21—* p-C6H13—Ph—*
pound
1332
Com- S S C10H21—* p-C7H15—Ph—*
pound
1333
Com- S S C10H21—* p-C8H17—Ph—*
pound
1334
Com- S S C10H21—* p-C9H19—Ph—*
pound
1335
Com- S S C10H21—* p-C10H21—Ph—*
pound
1336
Com- S S C10H21—* p-C11H23—Ph—*
pound
1337
Com- S S C10H21—* p-C12H25—Ph—*
pound
1338
Com- S S C10H21—* p-C13H27—Ph—*
pound
1339
Com- S S C10H21—* p-C14H29—Ph—*
pound
1340
Com- S S C10H21—* p-C15H31—Ph—*
pound
1341
Com- S S C10H21—* p-C16H33—Ph—*
pound
1342
Com- S S C10H21—* p-C17H35—Ph—*
pound
1343
Com- S S C10H21—* p-C18H37—Ph—*
pound
1344
Com- pound 1345 S S C12H25—*
Figure US10497881-20191203-C01260
Com- pound 1346 S S C12H25—*
Figure US10497881-20191203-C01261
Com- pound 1347 S S C12H25—*
Figure US10497881-20191203-C01262
Com- pound 1348 S S C12H25—*
Figure US10497881-20191203-C01263
Com- pound 1349 S S C12H25—*
Figure US10497881-20191203-C01264
Com- pound 1350 S S C12H25—*
Figure US10497881-20191203-C01265
Com- pound 1351 S S C12H25—*
Figure US10497881-20191203-C01266
Com- pound 1352 S S C12H25—*
Figure US10497881-20191203-C01267
TABLE 54
Xc1 Xc2 Rc11 Rc21
Compound 1353 S S C12H25—*
Figure US10497881-20191203-C01268
Compound 1354 S S C12H25—*
Figure US10497881-20191203-C01269
Compound 1355 S S C12H25—*
Figure US10497881-20191203-C01270
Compound 1356 S S C12H25—*
Figure US10497881-20191203-C01271
Compound 1357 S S C12H25—*
Figure US10497881-20191203-C01272
Compound 1358 S S C12H25—*
Figure US10497881-20191203-C01273
Compound 1359 S S
Figure US10497881-20191203-C01274
Figure US10497881-20191203-C01275
Compound 1360 S S
Figure US10497881-20191203-C01276
Figure US10497881-20191203-C01277
Compound 1361 S S
Figure US10497881-20191203-C01278
Figure US10497881-20191203-C01279
Compound 1362 S S
Figure US10497881-20191203-C01280
Figure US10497881-20191203-C01281
Compound 1363 S S
Figure US10497881-20191203-C01282
Figure US10497881-20191203-C01283
Compound 1364 S S
Figure US10497881-20191203-C01284
Figure US10497881-20191203-C01285
Compound 1365 S S
Figure US10497881-20191203-C01286
Figure US10497881-20191203-C01287
Compound 1366 S S
Figure US10497881-20191203-C01288
Figure US10497881-20191203-C01289
Compound 1367 S S
Figure US10497881-20191203-C01290
Figure US10497881-20191203-C01291
Compound 1368 S S
Figure US10497881-20191203-C01292
Figure US10497881-20191203-C01293
Compound 1369 S S
Figure US10497881-20191203-C01294
Figure US10497881-20191203-C01295
Compound 1370 S S
Figure US10497881-20191203-C01296
Figure US10497881-20191203-C01297
TABLE 55
Xc1 Xc2 Rc11 Rc21
Compound 1371 S S
Figure US10497881-20191203-C01298
Figure US10497881-20191203-C01299
Compound 1372 S S
Figure US10497881-20191203-C01300
Figure US10497881-20191203-C01301
Compound 1373 S S
Figure US10497881-20191203-C01302
Figure US10497881-20191203-C01303
Compound 1374 S S
Figure US10497881-20191203-C01304
Figure US10497881-20191203-C01305
Compound 1375 S S
Figure US10497881-20191203-C01306
Figure US10497881-20191203-C01307
Compound 1376 S S
Figure US10497881-20191203-C01308
Figure US10497881-20191203-C01309
Compound 1377 S S
Figure US10497881-20191203-C01310
Figure US10497881-20191203-C01311
Compound 1378 S S
Figure US10497881-20191203-C01312
Figure US10497881-20191203-C01313
Compound 1379 S S
Figure US10497881-20191203-C01314
Figure US10497881-20191203-C01315
Compound 1380 S S
Figure US10497881-20191203-C01316
Figure US10497881-20191203-C01317
Compound 1381 S S
Figure US10497881-20191203-C01318
Figure US10497881-20191203-C01319
Compound 1382 S S
Figure US10497881-20191203-C01320
Figure US10497881-20191203-C01321
Compound 1383 S S
Figure US10497881-20191203-C01322
Figure US10497881-20191203-C01323
Compound 1384 S S
Figure US10497881-20191203-C01324
Figure US10497881-20191203-C01325
Compound 1385 S S
Figure US10497881-20191203-C01326
Figure US10497881-20191203-C01327
Compound 1386 S S
Figure US10497881-20191203-C01328
Figure US10497881-20191203-C01329
Compound 1387 S S
Figure US10497881-20191203-C01330
Figure US10497881-20191203-C01331
Compound 1388 S S
Figure US10497881-20191203-C01332
Figure US10497881-20191203-C01333
TABLE 56
Xc1 Xc2 Xc11 Xc21
Compound 1389 S S
Figure US10497881-20191203-C01334
Figure US10497881-20191203-C01335
Compound 1390 S S
Figure US10497881-20191203-C01336
Figure US10497881-20191203-C01337
Compound 1391 S S
Figure US10497881-20191203-C01338
Figure US10497881-20191203-C01339
Compound 1392 S S
Figure US10497881-20191203-C01340
Figure US10497881-20191203-C01341
Compound 1393 S S
Figure US10497881-20191203-C01342
Figure US10497881-20191203-C01343
Compound 1394 S S
Figure US10497881-20191203-C01344
Figure US10497881-20191203-C01345
Compound 1395 S S
Figure US10497881-20191203-C01346
Figure US10497881-20191203-C01347
Compound 1396 S S
Figure US10497881-20191203-C01348
Figure US10497881-20191203-C01349
Compound 1397 S S
Figure US10497881-20191203-C01350
Figure US10497881-20191203-C01351
Compound 1398 S S
Figure US10497881-20191203-C01352
Figure US10497881-20191203-C01353
Compound 1399 S S
Figure US10497881-20191203-C01354
Figure US10497881-20191203-C01355
Compound 1400 O O C5H11—* C5H11—*
Compound 1401 O O C6H13—* C6H13—*
Compound 1402 O O C7H15—* C7H15—*
Compound 1403 O O C8H17—* C8H17—*
Compound 1404 O O C9H19—* C9H19—*
Compound 1405 O O C10H21—* C10H21—*
Compound 1406 O O C11H23—* C11H23—*
Compound 1407 O O C12H25—* C12H25—*
Compound 1408 O O C13H27—* C13H27—*
Compound 1409 O O C14H29—* C14H29—*
Compound 1410 O O C15H31—* C15H31—*
Compound 1411 O O C16H33—* C16H33—*
Compound 1412 O O C17H35—* C17H35—*
Compound 1413 O O C18H37—* C18H37—*
Compound 1414 O O p-C5H11—Ph—* p-C5H11—Ph—*
Compound 1415 O O p-C6H13—Ph—* p-C6H13—Ph—*
Compound 1416 O O p-C7H15—Ph—* p-C7H15—Ph—*
Compound 1417 O O p-C8H17—Ph—* p-C8H17—Ph—*
Compound 1418 O O p-C9H19—Ph—* p-C9H19—Ph—*
Compound 1419 O O p-C10H21—Ph—* p-C10H21—Ph—*
Compound 1420 O O p-C11H23—Ph—* p-C11H23—Ph—*
Compound 1421 O O p-C12H25—Ph—* p-C12H25—Ph—*
TABLE 57
Xc1 Xc2 Rc11 Rc21
Com- O O p-C13H27—Ph—* p-C13H27—Ph—*
pound
1422
Com- O O p-C14H29—Ph—* p-C14H29—Ph—*
pound
1423
Com- O O p-C15H31—Ph—* p-C15H31—Ph—*
pound
1424
Com- O O p-C16H33—Ph—* p-C16H33—Ph—*
pound
1425
Com- O O p-C17H35—Ph—* p-C17H35—Ph—*
pound
1426
Com- O O p-C18H37—Ph—* p-C18H37—Ph—*
pound
1427
Com- pound 1428 O O
Figure US10497881-20191203-C01356
Figure US10497881-20191203-C01357
Com- pound 1429 O O
Figure US10497881-20191203-C01358
Figure US10497881-20191203-C01359
Com- pound 1430 O O
Figure US10497881-20191203-C01360
Figure US10497881-20191203-C01361
Com- pound 1431 O O
Figure US10497881-20191203-C01362
Figure US10497881-20191203-C01363
Com- pound 1432 O O
Figure US10497881-20191203-C01364
Figure US10497881-20191203-C01365
Com- pound 1433 O O
Figure US10497881-20191203-C01366
Figure US10497881-20191203-C01367
Com- pound 1434 O O
Figure US10497881-20191203-C01368
Figure US10497881-20191203-C01369
Com- pound 1435 O O
Figure US10497881-20191203-C01370
Figure US10497881-20191203-C01371
Com- pound 1436 O O
Figure US10497881-20191203-C01372
Figure US10497881-20191203-C01373
Com- pound 1437 O O
Figure US10497881-20191203-C01374
Figure US10497881-20191203-C01375
Com- pound 1438 O O
Figure US10497881-20191203-C01376
Figure US10497881-20191203-C01377
Com- pound 1439 O O
Figure US10497881-20191203-C01378
Figure US10497881-20191203-C01379
Com- pound 1440 O O
Figure US10497881-20191203-C01380
Figure US10497881-20191203-C01381
Com- pound 1441 O O
Figure US10497881-20191203-C01382
Figure US10497881-20191203-C01383
Com- S S C4H3OC4H8—* C4H3OC4H8—*
pound
1442
Com- S S C2H5OC2H4—* C2H5OC2H4—*
pound
1443
TABLE 58
Xc1 Xc2 Rc11 Rc12
Compound 1444 S S C6H13OC4H8—* C6H13OC4H8—*
Compound 1445 S S C2H5OC4H8—* C2H5OC4H8—*
Compound 1446 S S CH3OC3H6—* CH3OC3H6—*
Compound 1447 S S
Figure US10497881-20191203-C01384
Figure US10497881-20191203-C01385
Compound 1448 S S
Figure US10497881-20191203-C01386
Figure US10497881-20191203-C01387
Compound 1449 S S
Figure US10497881-20191203-C01388
Figure US10497881-20191203-C01389
Compound 1450 S S PhC3H6—* PhC3H6—*
Compound 1451 S S PhOC3H6—* PhOC3H6—*
Compound 1452 S S
Figure US10497881-20191203-C01390
Figure US10497881-20191203-C01391
Compound 1453 S S
Figure US10497881-20191203-C01392
Figure US10497881-20191203-C01393
Compound 1454 S S
Figure US10497881-20191203-C01394
Figure US10497881-20191203-C01395
Compound 1455 S S
Figure US10497881-20191203-C01396
Figure US10497881-20191203-C01397
Compound 1456 S S
Figure US10497881-20191203-C01398
Figure US10497881-20191203-C01399
Compound 1457 S S 3,7-Dimethyloctyl 3,7-Dimethyloctyl
Compound 1458 S S 3,7-Dimethyloctyl H
Compound 1459 S S 2-Ethylhexyl 2-Ethylhexyl
Compound 1460 S S
Figure US10497881-20191203-C01400
Figure US10497881-20191203-C01401
Compound 1461 S S
Figure US10497881-20191203-C01402
Figure US10497881-20191203-C01403
TABLE 59
Xc1 Xc2 Rc11 Rc21
Compound 1462 S S
Figure US10497881-20191203-C01404
Figure US10497881-20191203-C01405
Compound 1463 S S
Figure US10497881-20191203-C01406
 		H
Compound 1464 S S
Figure US10497881-20191203-C01407
Figure US10497881-20191203-C01408
Compound 1465 S S C5H11—*
Figure US10497881-20191203-C01409
Compound 1466 S S
Figure US10497881-20191203-C01410
Figure US10497881-20191203-C01411
Compound 1467 S S
Figure US10497881-20191203-C01412
Figure US10497881-20191203-C01413
Compound 1468 S S
Figure US10497881-20191203-C01414
Figure US10497881-20191203-C01415
Compound 1469 S S
Figure US10497881-20191203-C01416
Figure US10497881-20191203-C01417
Compound 1470 S S
Figure US10497881-20191203-C01418
Figure US10497881-20191203-C01419
Compound 1471 S S
Figure US10497881-20191203-C01420
 		H
Compound 1472 S S
Figure US10497881-20191203-C01421
Figure US10497881-20191203-C01422
Compound 1473 S S
Figure US10497881-20191203-C01423
Figure US10497881-20191203-C01424
Compound 1474 S S
Figure US10497881-20191203-C01425
Figure US10497881-20191203-C01426
Compound 1475 S S
Figure US10497881-20191203-C01427
Figure US10497881-20191203-C01428
In the organic semiconductor layer of the organic semiconductor element according to the present invention or the organic semiconductor film according to the present invention described below, the content of the specific compound is preferably 30 to 100 mass %, more preferably 50 to 100 mass %, and even more preferably 70 to 100 mass %. In a case where a binder polymer described below is not contained, the content is preferably 90 to 100 mass % and more preferably 95 to 100 mass %.
<Binder Polymer>
The organic semiconductor layer of the organic semiconductor element according to the present invention preferably contains the binder polymer.
The organic semiconductor element according to the present invention may be an organic semiconductor element having a layer including the organic semiconductor layer and the binder polymer.
The types of the binder polymer are not particularly limited, and well-known binder polymers can be used.
Examples of the binder polymer include a polystyrene resin, an acrylic resin, rubber, and a thermoplastic elastomer.
Among these, as the binder polymer, a polymer compound (a polymer having a monomer unit having a benzene ring group) having a benzene ring is preferable. The content of the monomer unit having a benzene ring group is not particularly limited. However, the content is preferably 50 mol % or greater, more preferably 70 mol % or greater, and even more preferably 90 mol % or greater with respect to the entire monomer unit. The upper limit is not particularly limited, but examples of the upper limit include 100 mol %.
Examples of the binder polymer include polystyrene, poly(α-methylstyrene), polyvinyl cinnamate, poly(4-vinylphenyl), and poly(4-methylstyrene).
A weight-average molecular weight of the binder polymer is not particularly limited, but is preferably 1,000 to 2,000,000, more preferably 3,000 to 1,000,000, and even more preferably 5,000 to 600,000.
In a case where a solvent described below is used, it is preferable that the binder polymer exhibits solubility higher than the solubility of the specific compound in a used solvent. If the above aspect is adopted, mobility and heat stability of the obtained organic semiconductor are further improved.
A content of the binder polymer in the organic semiconductor layer of the organic semiconductor element of the present invention is preferably 1 to 200 parts by mass, more preferably 10 to 150 parts by mass, and even more preferably 20 to 120 parts by mass with respect to 100 parts by mass of the content of the specific compound. If the content is within the above range, mobility and heat stability of the obtained organic semiconductor are further improved.
<Other Components>
Other components may be included other than the specific compound and the binder polymer may be included in the organic semiconductor layer according to the organic semiconductor element of the present invention.
As other components, known additives and the like can be used.
In the organic semiconductor layer, a content of the components other than the specific compound and the binder polymer is preferably 10 mass % or less, more preferably 5 mass % or less, even more preferably 1 mass % or less, and particularly preferably 0.1 mass % or less. If the content of other components is within the above range, film formability is improved, and mobility and heat stability of the obtained organic semiconductor are further improved.
(Method of Forming Organic Semiconductor Layer)
The method of forming the organic semiconductor layer according to the organic semiconductor element of the present invention is not particularly limited. However, a desired organic semiconductor layer can be formed by applying the composition for forming the organic semiconductor film according to the present invention described below to a source electrode, a drain electrode, and a gate insulating film and performing a drying treatment, if necessary.
(Method of Manufacturing Organic Semiconductor Element and Organic Semiconductor Film)
The organic semiconductor element and an organic semiconductor film of the present invention is preferably manufactured using the composition for forming an organic semiconductor film of the present invention described below.
A method of manufacturing an organic semiconductor film or an organic semiconductor element by using the composition for forming an organic semiconductor film of the present invention is not particularly limited, and known methods can be adopted. Examples thereof include a method of manufacturing an organic semiconductor film by applying the composition onto a predetermined base material and if necessary, performing a drying treatment.
The method of applying the composition onto a base material is not particularly limited, and known methods can be adopted. Examples thereof include an ink jet printing method, a flexographic printing method, a bar coating method, a spin coating method, a knife coating method, a doctor blade method, and the like. Among these, an ink jet printing method and a flexographic printing method are preferable.
Preferred examples of the flexographic printing method include an aspect in which a photosensitive resin plate is used as a flexographic printing plate. By printing the composition onto a substrate according to the aspect, a pattern can be easily formed.
Among these, the method of manufacturing an organic semiconductor element and an organic semiconductor film according to the present invention preferably include an applying step of applying an composition for forming an organic semiconductor film according to the present invention to a substrate and a removing step of removing at least a portion of a solvent having a boiling point of 100° C. or higher included in the composition for forming the organic semiconductor film.
<Solvent Having Boiling Point of 100° C. or Higher>
The composition for forming the organic semiconductor film according to the present invention contains a solvent having a boiling point of 100° C. or higher (hereinafter, referred to a “specific solvent”).
Examples of the specific solvent include a hydrocarbon-based solvent such as octane, decane, toluene, xylene, mesitylene, ethylbenzene, decalin, 1-methylnaphthalene, tetralin, and dimethyltetralin, a ketone-based solvent such as methyl isobutyl ketone and cyclohexanone, a halogenated hydrocarbon-based solvent such as tetrachloroethane, chlorobenzene, dichlorobenzene, chlorotoluene, 1-fluoronaphthalene, and 1-chloronaphthalene, an ester-based solvent such as butyl acetate and amyl acetate, an alcohol-based solvent such as butanol, pentanol, hexanol, cyclohexanol, methyl cellosolve, ethyl cellosolve, and ethylene glycol, an ether-based solvent such as dibutyl ether, dioxane, anisole, 4-tertiary butyl anisole, and m-dimethoxybenzene, an amide-based solvent such as N,N-dimethylformamide and N,N-dimethylacetamide, an imide-based solvent such as 1-methyl-2-pyrrolidone and 1-methyl-2-imidazolidinone, a sulfoxide-based solvent such as dimethyl sulfoxide, and a nitrile-based solvent such as butyronitrile and benzonitrile.
The specific solvent may be used singly or two or more types thereof may be used in combination.
Among these, a hydrocarbon-based solvent, a halogenated hydrocarbon-based solvent and/or an ether-based solvent are preferable, toluene, xylene, mesitylene, tetralin, dichlorobenzene, or anisole is more preferable, and toluene is even more preferable.
If the specific solvent is the aforementioned solvent, coating properties are excellent, and thus an organic semiconductor film can be easily formed.
In view of stability of the composition for forming the organic semiconductor film, forming an even film, and drying, the boiling point of the specific solvent in normal pressure is 100° C. or higher, preferably 100° C. to 300° C., more preferably 100° C. to 200° C., and even more preferably 100° C. to 150° C.
The drying treatment in the removing step is a treatment performed if necessary, and the optimal treatment conditions are suitably selected according to the type of the specific compound used and the solvent. In view of further improving mobility and heat stability of the obtained organic semiconductor and improving productivity, a heating temperature is preferably 30° C. to 100° C. and more preferably 40° C. to 80° C., and a heating time is preferably 10 to 300 minutes and more preferably 30 to 180 minutes.
A thickness of the formed organic semiconductor layer is not particularly limited. From the viewpoint of mobility and heat stability of the obtained organic semiconductor, the film thickness is preferably 10 to 500 nm and more preferably 30 to 200 nm.
<Organic Semiconductor Element>
The organic semiconductor element is not particularly limited, but is preferably an organic semiconductor element having 2 to 5 terminals, and more preferably an organic semiconductor element having 2 or 3 terminals.
It is preferable that the organic semiconductor element is not a photoelectric conversion element.
The organic semiconductor element according to the present invention is preferably a non-luminous organic semiconductor element.
Examples of a 2-terminal element include a rectifier diode, a constant voltage diode, a PIN diode, a Schottky barrier diode, a surge protection diode, a diac, a varistor, a tunnel diode, and the like.
Examples of a 3-terminal element include a bipolar transistor, a Darlington transistor, a field effect transistor, insulated gate bipolar transistor, a uni-junction transistor, a static induction transistor, a gate turn-off thyristor, a triac, a static induction thyristor, and the like.
Among these, a rectifier diode and transistors are preferable, and a field effect transistor is more preferable.
An aspect of the organic thin film transistor of the present invention will be described with reference to drawings.
FIG. 1 is a schematic cross-sectional view of an aspect of an organic semiconductor element (organic thin film transistor (organic TFT)) of the present invention.
In FIG. 1, an organic thin film transistor 100 includes a substrate 10, a gate electrode 20 disposed on the substrate 10, a gate insulating film 30 covering the gate electrode 20, a source electrode 40 and a drain electrode 42 which contact a surface of the gate insulating film 30 that is on the side opposite to the gate electrode 20 side, an organic semiconductor film 50 covering a surface of the gate insulating film 30 between the source electrode 40 and the drain electrode 42, and a sealing layer 60 covering each member. The organic thin film transistor 100 is a bottom gate-bottom contact type organic thin film transistor.
In FIG. 1, the organic semiconductor film 50 corresponds to a film formed of the composition described above.
Hereinafter, the substrate, the gate electrode, the gate insulating film, the source electrode, the drain electrode, the organic semiconductor film, the sealing layer, and methods for forming each of these will be specifically described.
<Substrate>
The substrate plays a role of supporting the gate electrode, the source electrode, the drain electrode, and the like which will be described later.
The type of the substrate is not particularly limited, and examples thereof include a plastic substrate, a glass substrate, a ceramic substrate, and the like. Among these, from the viewpoint of applicability to each device and costs, a glass substrate or a plastic substrate is preferable.
Examples of materials of the plastic substrate include a thermosetting resin (for example, an epoxy resin, a phenol resin, a polyimide resin, or a polyester resin (for example, polyethylene terephthalate (PET) or polyethylene naphthalate (PEN)) and a thermoplastic resin (for example, a phenoxy resin, a polyethersulfone, polysulfone, or polyphenylene sulfone).
Examples of materials of the ceramic substrate include alumina, aluminum nitride, zirconia, silicon, silicon nitride, silicon carbide, and the like.
Examples of materials of the glass substrate include soda lime glass, potash glass, borosilicate glass, quartz glass, aluminosilicate glass, lead glass, and the like.
<Gate Electrode, Source Electrode, and Drain Electrode>
Examples of materials of the gate electrode, the source electrode, and the drain electrode include a metal such as gold (Au), silver, aluminum (Al), copper, chromium, nickel, cobalt, titanium, platinum, tantalum, magnesium, calcium, barium, or sodium; a conductive oxide such as InO2, SnO2, or indium tin oxide (ITO); a conductive polymer such as polyaniline, polypyrrole, polythiophene, polyacetylene, or polydiacetylene; a semiconductor such as silicon, germanium, or gallium arsenide; a carbon material such as fullerene, carbon nanotubes, or graphite; and the like. Among these, a metal is preferable, and silver and aluminum are more preferable.
A thickness of each of the gate electrode, the source electrode, and the drain electrode is not particularly limited, but is preferably 20 to 200 nm.
A method of forming the gate electrode, the source electrode, and the drain electrode is not particularly limited, but examples thereof include a method of vacuum vapor-depositing or sputtering an electrode material onto a substrate, a method of coating a substrate with a composition for forming an electrode, a method of printing a composition for forming an electrode onto a substrate, and the like. Furthermore, in a case where the electrode is patterned, examples of the patterning method include a photolithography method; a printing method such as ink jet printing, screen printing, offset printing, or relief printing; a mask vapor deposition method; and the like.
<Gate Insulating Film>
Examples of materials of the gate insulating film include a polymer such as polymethyl methacrylate, polystyrene, polyvinylphenol, polyimide, polycarbonate, polyester, polyvinylalcohol, polyvinyl acetate, polyurethane, polysulfone, polybenzoxazole, polysilsesquioxane, an epoxy resin, or a phenol resin; an oxide such as silicon dioxide, aluminum oxide, or titanium oxide; a nitride such as silicon nitride; and the like. Among these materials, in view of the compatibility with the organic semiconductor film, a polymer is preferable.
In a case where a polymer is used as the material of the gate insulating film, it is preferable to use a cross-linking agent (for example, melamine) in combination. If the cross-linking agent is used in combination, the polymer is cross-linked, and durability of the formed gate insulating film is improved.
A film thickness of the gate insulating film is not particularly limited, but is preferably 100 to 1,000 nm.
A method of forming the gate insulating film is not particularly limited, but examples thereof include a method of coating a substrate, on which the gate electrode is formed, with a composition for forming a gate insulating film, a method of vapor-depositing or sputtering the material of the gate insulating film onto a substrate on which the gate electrode is formed, and the like. A method of coating the aforementioned substrate with the composition for forming a gate insulating film is not particularly limited, and it is possible to use a known method (a bar coating method, a spin coating method, a knife coating method, or a doctor blade method).
In a case where the gate insulating film is formed by coating the substrate with the composition for forming a gate insulating film, for the purpose of removing the solvent, causing cross-linking, or the like, the composition may be heated (baked) after coating.
<Organic Semiconductor Film>
The organic semiconductor film according to the present invention is a film formed of the composition for forming the organic semiconductor film according to the present invention.
The method of forming the organic semiconductor film is not particularly limited. A desired organic semiconductor film can be formed by applying the aforementioned composition to a source electrode, a drain electrode, and a gate insulating film and performing a drying treatment, if desired.
<Binder Polymer Layer>
The organic semiconductor element of the present invention preferably has a layer of the aforementioned binder polymer between the aforementioned organic semiconductor layer and an insulating film, and more preferably has a layer of the aforementioned binder polymer between the aforementioned organic semiconductor layer and the gate insulating film. A film thickness of the binder polymer layer is not particularly limited, but is preferably 20 to 500 nm. The binder polymer layer should be a layer containing the aforementioned polymer, and is preferably a layer composed of the aforementioned binder polymer.
A method of forming the binder polymer layer is not particularly limited, and a known method (a bar coating method, a spin coating method, a knife coating method, a doctor blade method, or an ink jet method) can be used.
In a case where the binder polymer layer is formed by performing coating by using a composition for forming a binder polymer layer, for the purpose of removing a solvent, causing cross-linking, or the like, the composition may be heated (baked) after coating.
<Sealing Layer>
From the viewpoint of durability, the organic semiconductor element of the present invention preferably includes a sealing layer as an outermost layer. In the sealing layer, a known sealant can be used.
A thickness of the sealing layer is not particularly limited, but is preferably 0.2 to 10 μm.
A method of forming the sealing layer is not particularly limited, but examples thereof include a method of coating a substrate, on which the gate electrode, the gate insulating film, the source electrode, the drain electrode, and the organic semiconductor film are formed, with a composition for forming a sealing layer, and the like. Specific examples of the method of coating the substrate with the composition for forming a sealing layer are the same as the examples of the method of coating the substrate with the composition for forming a gate insulating film. In a case where the organic semiconductor film is formed by coating the substrate with the composition for forming a sealing layer, for the purpose of removing the solvent, causing cross-linking, or the like, the composition may be heated (baked) after coating.
FIG. 2 is a schematic cross-sectional view of another aspect of the organic semiconductor element (organic thin film transistor) of the present invention.
In FIG. 2, an organic thin film transistor 200 includes the substrate 10, the gate electrode 20 disposed on the substrate 10, the gate insulating film 30 covering the gate electrode 20, the organic semiconductor film 50 disposed on the gate insulating film 30, the source electrode 40 and the drain electrode 42 disposed on the organic semiconductor film 50, and the sealing layer 60 covering each member. Herein, the source electrode 40 and the drain electrode 42 are formed using the aforementioned composition of the present invention. The organic thin film transistor 200 is a top contact type organic thin film transistor.
The substrate, the gate electrode, the gate insulating film, the source electrode, the drain electrode, the organic semiconductor film, and the sealing layer are as described above.
In FIGS. 1 and 2, the aspects of the bottom gate-bottom contact type organic thin film transistor and the bottom gate-top contact type organic thin film transistor were specifically described. However, the organic semiconductor element of the present invention can also suitably used in a top gate-bottom contact type organic thin film transistor and a top gate-top contact type organic thin film transistor.
The organic thin film transistor described above can be suitably used for electronic paper and a display device.
(Composition for Forming Organic Semiconductor Film)
The composition for forming the organic semiconductor film according to the present invention contains a solvent having a boiling point of 100° C. or higher and a compound represented by Formula 1, and a content of the compound represented by Formula 1 is 20 mass % or less with respect to a total amount of the composition for forming the organic semiconductor film.
The composition for forming the organic semiconductor film according to the present invention preferably contains a binder polymer.
The specific compound, the binder polymer, and the solvent in the composition for forming the organic semiconductor film according to the present invention are the same as the aforementioned specific compound, the aforementioned binder polymer, and the aforementioned solvent, and preferable aspects are also the same.
The content of the specific compound of the composition for forming the organic semiconductor film according to the present invention is 20 mass % or less, preferably 0.001 to 15 mass %, and more preferably 0.01 to 10 mass % with respect to the total amount of the composition for forming the organic semiconductor film. In a case where two or more types of specific compounds are used in combination, the total content of the specific compounds is preferably in the range described above. If the content of the specific compound is in the range described above, the organic semiconductor element having high mobility and high driving stability can be obtained, storage stability of the composition for forming the organic semiconductor film is also satisfactory.
The content of the specific compound is preferably 30 to 100 mass %, more preferably 50 to 100 mass %, and even more preferably 70 to 100 mass % with respect to the total solid content of the composition for forming the organic semiconductor film. In a case where a binder polymer described below is not contained, the total content is preferably 90 to 100 mass % and more preferably 95 to 100 mass %. The solid content is an amount of the component except for the volatile component such as the solvent.
The content of the binder polymer in the composition for forming the organic semiconductor film according to the present invention is preferably greater than 0 mass % and 20 mass % or less, more preferably 0.01 to 15 mass %, and even more preferably 0.25 to 10 mass % with respect to the total amount of the composition for forming the organic semiconductor film. If the content is in the range described above, mobility and heat resistance of the obtained organic semiconductor become more excellent.
The composition for forming the organic semiconductor film according to the present invention may include other component in addition to the specific compound and the binder polymer.
As the component, well-known additives may be used.
The content of the component in addition to the specific compound and the binder polymer in the composition for forming the organic semiconductor film according to the present invention is preferably 10 mass % or less, more preferably 5 mass % or less, even more preferably 1 mass % or less, and particularly preferably 0.1 mass % or less with respect to the total solid content. If the content is in the range described above, film formability is improved, and mobility and heat stability of the obtained organic semiconductor are further improved.
The viscosity of the composition for forming the organic semiconductor film according to the present invention is not particularly limited. However, in view of excellent coating properties, the viscosity is preferably 3 to 100 mPa·s, more preferably 5 to 50 mPa·s, and even more preferably 9 to 40 mPa·s. The viscosity according to the present invention refers to viscosity at 25° C.
As a method of measuring the viscosity, a measuring method in conformity of JIS Z8803 is preferable.
The method of manufacturing the composition for forming the organic semiconductor film according to the present invention is not particularly limited, and well-known methods can be applied. For example, a desired composition can be obtained by adding a specific amount of a specific compound in the solvent and applying an suitable stirring treatment. In a case where the binder polymer is used, the specific compound and the binder polymer are simultaneously or sequentially added, so as to suitably manufacture the composition.
EXAMPLES
Hereinafter, the present invention will be more specifically described based on examples. The materials and the amount thereof used, the proportion of the materials, the content and procedure of treatments, and the like described in the following examples can be suitably changed within a scope that does not depart from the gist of the present invention. Accordingly, the scope of the present invention is not limited to the following specific examples. Herein, unless otherwise specified, “part” and “%” are based on mass.
Specific Compounds and Synthesis Examples
Structures of E-1 to E-10 used in the examples and C-1 to C-2 used in the comparative examples are provided below.
Figure US10497881-20191203-C01429
<Synthesis of E-1>
An intermediate M1 was synthesized according to a scheme X1 below.
Figure US10497881-20191203-C01430
The intermediate M1 and octyl zinc chloride were fused by negishi coupling reaction, so as to synthesize a compound E-1.
Figure US10497881-20191203-C01431
<Synthesis of E-2 to E-10>
E-2 to E-10 were also synthesized in the same manner as in E-1, except for changing an organic zinc compound fused with the intermediate M1 to suitable compounds.
<Synthesis of C-1>
A compound C-1 was synthesized according to the method described in JP2010-177637A.
<Synthesis of C-2>
A compound C-2 was synthesized according to the method disclosed in WO2013/168048A.
Examples 1 to 10 and Comparative Examples 1 to 2
<Manufacturing of TFT Element>
The specific compound presented in Table 60 or a comparative compound (1 mg) and toluene (1 mL) were mixed with each other and heated to 100° C., and the composition for forming the organic semiconductor film was obtained.
An organic semiconductor film was formed by casting this composition to a substrate for measuring FET characteristics which was heated to 90° C. under the nitrogen atmosphere, and an organic thin film transistor element for measuring FET characteristics was obtained. As the substrate for measuring FET characteristics, a silicon substrate in a bottom gate-bottom contact structure including chromium/gold (gate width W=100 mm, gate length L=100 μm) arranged in a comb-shape as source and drain electrodes and SiO2 (film thickness: 200 nm) as an insulating film was used.
The obtained composition was applied to a substrate for measuring FET characteristics by flexographic printing. Specifically, a flexographic printability test machine F1 (manufactured by IGT Testing Systems) was used as a printing machine, and AFP DSH 1.70% (manufactured by Asahi Kasei Corporation)/a solid image was used as a flexographic resin version. After printing was performed in a pressure between a plate and a substrate of 60 N and a transportation speed of 0.4 m/second, drying was performed at 40° C. for two hours, so as to form an organic semiconductor film, and an organic thin film transistor element (organic TFT element) for measuring FET characteristics was obtained.
As the substrate for measuring FET characteristics, a silicon substrate in a bottom gate-bottom contact structure including chromium/gold (gate width W=100 mm, gate length L=100 μm) arranged in a comb-shape as source and drain electrodes and SiO2 (film thickness: 200 nm) as an insulating film was used.
The ink was applied to the substrate for measuring FET characteristics by ink jet printing. Specifically, DPP2831 (manufactured by FUJIFILM Global Graphic Systems Co., Ltd.) was used as an inkjet device and 10 pL heads were used, so as to form a solid film with a jetting frequency of 2 Hz and a pitch between dots of 20 μm. Thereafter, drying was performed for one hour at 70° C., so as to form an organic semiconductor film, and the organic TFT element for measuring FET characteristics was obtained.
In the examples and the comparative examples, evaluations of mobility, coating film formability, and heat resistance described below with respect to the organic TFT element obtained by ink jet printing were the same as those of the organic TFT element obtained by casting the composition.
<Carrier Mobility (Mobility)>
With respect to the FET characteristics of the organic thin film transistor elements of the respective examples and the respective comparative examples, carrier mobility was evaluated under normal pressure and the nitrogen atmosphere by employing a semiconductor parameter analyzer (manufactured by Agilent, 4156C) to which a semi automatic prober (manufactured by Vector Semiconductor Co., Ltd., AX-2000) was connected.
A voltage of −80 V was applied between source electrodes and drain electrodes of the respective organic thin film transistor elements (FET elements), a gate voltage was changed in the range of 20 V to −100 V, an equation below presenting a drain current Id was used, so as to calculate carrier mobility μ.
Id=(w/2L)μCi(Vg−Vth)2
In the equation, L represents a gate length, W represents a gate width, Ci represents capacitance of the insulating layer per unit area, Vg represents a gate voltage, and Vth represents a threshold voltage. The numerical value of the carrier mobility is required to be practically 0.01 or greater, preferably 0.1 or greater, and more preferably 0.3 or greater.
The expression “no characteristics” in the tables presents the created element did not have TFT characteristics.
<Coating Film Formability>
The compound according to the present invention or the comparative compound (5 mg) and toluene (1 mL) were mixed and heated to 100° C., so as to obtain a non-luminescent organic semiconductor solution. This coating liquid was casted under nitrogen atmosphere to the entire surface of the substrate which was heated to 90° C. and on which channels for 50 elements were formed, so as to form an organic semiconductor thin film, and 50 organic thin film transistor elements for measuring FET characteristics were obtained. Evaluation standards of the coating film formability were set as below, and the evaluation results were presented in Table 60.
[Evaluation standard] A: 45 or more elements out of the obtained 50 elements were driven as organic thin film transistor element
B: Less than 45 elements out of the obtained 50 elements were driven as organic thin film transistor element
<Heat Resistance>
After the manufactured respective organic thin film transistor elements were heated for one hour at 130° C. in a nitrogen glove box, carrier mobility μ was measured, so as to calculate a carrier mobility maintenance rate after heating by the equation below.
Carrier mobility maintenance rate after heating (%)=Carrier mobility (after heating)/carrier mobility (initial value)×100
Obtained results were evaluated according to evaluation standards below. The evaluation results are presented in Table 60. The expression “N/A” in the table means that a heat resistance was not performed since a created element did not have TFT characteristics.
[Evaluation Standard]
A: Carrier mobility maintenance rate after heating was 95% or greater
B: Carrier mobility maintenance rate after heating was 70% or greater and less than 95%
C: Carrier mobility maintenance rate after heating was 40% or greater and less than 70%
D: Carrier mobility maintenance rate after heating was 20% or greater and less than 40%
E: Carrier mobility maintenance rate after heating was less than 20%
TABLE 60
Specific Solu- Coating film Heat
compound Mobility bility formability resistance
Example 1 E-1 1.1 A A A
Example 2 E-2 1 B A A
Example 3 E-3 0.5 A A A
Example 4 E-4 0.7 B A A
Example 5 E-5 0.6 A A B
Example 6 E-6 0.3 A A A
Example 7 E-7 0.05 B A A
Example 8 E-8 0.03 B A B
Example 9 E-9 0.03 C A A
Example 10 E-10 0.01 B A A
Comparative C-1 No C B N/A
Example 1 Charac-
teristics
Comparative C-2 5 × 10−3 C B D
Example 2
Examples 11 to 16, Comparative Examples 3 to 4
<Manufacturing of TFT Elements>
Respective evaluations were performed in the same manner as in Examples 1 to 10 and Comparative Examples 1 to 2 except for mixing the specific compound of the present invention or the comparative compound presented in Table 61, the binder polymer presented in Table 61, and the solvent presented in Table 61 in the concentrations presented in Table 61, performing heating to 100° C., and using the resultant as the composition for forming the organic semiconductor film. The respective evaluation results are presented in Table 61.
Abbreviations used in Table 61 are as below.
    • PαMS: Poly(α-methylstyrene), Mw=300,000, manufactured by Sigma-Aldrich Co. LLC.)
    • THF: Tetrahydrofuran
TABLE 61
Concentration
Concentration of of binder
semiconductor in polymer in Coating
Specific Binder composition composition Heat film
compound polymer Solvent (mass %) (mass %) Mobility resistance formability
Example 11 E-1 PαMS Toluene 0.5 0.5 1.2 A A
Example 12 E-2 PαMS Toluene 0.5 0.5 1.2 A A
Example 13 E-5 PαMS Toluene 0.5 0.5 0.8 A A
Example 14 E-6 PαMS Toluene 0.5 0.5 0.5 A A
Example 15 E-1 PαMS THF 0.5 0.5 0.1 B A
Example 16 E-1 PαMS Toluene 0.5 12.0 0.02 B A
Comparative C-1 PαMS Toluene 0.5 0.5 2 × 10−3 D B
Example 3
Comparative C-2 PαMS Toluene 0.5 0.5 No N/A B
Example 4 characteristics
Comparative Examples 5 to 21
The organic semiconductor films were formed in the same manner as in Example 1 to 16 except for weighing the specific compounds and toluene (1 mL) presented in Tables 60 and 61 and further the binder polymer (5 mg) in the examples presented in Table 61 such that the content of the respective specific compounds become 21 mass %, performing mixture, performing heating to 100° C., and using the resultant as the composition for forming the organic semiconductor film. However, in all of Comparative Examples 5 to 21, due to insoluble matters, various defects were generated, and thus TFT characteristics were not exhibited.
EXPLANATION OF REFERENCES
    • 10: substrate
    • 20: gate electrode
    • 30: gate insulating film
    • 40: source electrode
    • 42: drain electrode
    • 50: organic semiconductor film
    • 60: sealing layer
    • 100,200: organic thin film transistor

Claims (39)

What is claimed is:
1. An organic semiconductor element comprising:
a compound represented by Formula 1 below in an organic semiconductor layer:
Figure US10497881-20191203-C01432
wherein, in Formula 1, X11 and X12 each independently represent a chalcogen atom, Z1a to Z1j each independently represent a hydrogen atom or a halogen atom, A11 represents ═CRA11— or a nitrogen atom, RA11 represents a hydrogen atom or a group represented by R11, A12 represents ═CRA12— or a nitrogen atom, RA12 represents a hydrogen atom or a group represented by R12, n1 represents 0 or 1, p1 represents an integer of 0 to 2 in a case where A11 is ═CRA11— and represents 0 or 1 in a case where A11 is a nitrogen atom, q1 represents an integer of 0 to 2 in a case where A12 is ═CRA12— and represents 0 or 1 in a case where A12 is a nitrogen atom, at least one of p1 or q1 is not 0, R11 and R12 each independently represent a halogen atom, an aryl group, a heteroaryl group, or a group represented by Formula W below:

—SW-LW-TW  (W)
wherein, in Formula W, SW represents a single bond or an alkylene group represented by —(CRS 2)k—, RS each independently represent a hydrogen atom or a halogen atom, k represents an integer of 1 to 17, LW represents a single bond, a divalent linking group represented by any one of Formulae L-1 to L-16 below, or a group obtained by bonding any two or more of divalent linking groups represented by Formulae L-1 to L-16 below, TW represents an alkyl group, a cyano group, a vinyl group, an ethynyl group, an aryl group, a heteroaryl group, an oxyethylene group, an oligooxyethylene group of which the repetition number of oxyethylene units is two or greater, an oligosiloxane group having two or more silicon atoms, or a trialkylsilyl group, and
Figure US10497881-20191203-C01433
Figure US10497881-20191203-C01434
wherein, in Formulae L-1 to L-16, * and wavy line portions represent bonding positions to other structures, p13 represents an integer of 0 to 4, p14, p15, and p16 each independently represent an integer of 0 to 2, RL1, RL21, RL22, RL13, RL14, RL15, and RL16 each independently represent a hydrogen atom or a substituent.
2. The organic semiconductor element according to claim 1, wherein all of Z1a to Z1j are hydrogen atoms.
3. The organic semiconductor element according to claim 1, wherein n1 is not 0.
4. The organic semiconductor element according to claim 1, wherein:
at least one of R11 or R12 is a group represented by Formula W.
5. The organic semiconductor element according to claim 1, wherein p1 and q1 are 1.
6. The organic semiconductor element according to claim 1, wherein both of X11 and X12 are S atoms, A11 is ═CRA11—, and A12 is ═CRA12—.
7. The organic semiconductor element according to claim 1, wherein a compound represented by Formula 1 is a compound represented by Formula 2 below:
Figure US10497881-20191203-C01435
wherein, in Formula 2, X21 and X22 each independently represent a chalcogen atom, W21 and W22 each independently represent a group represented by Formula W.
8. The organic semiconductor element according to claim 1, wherein the compound represented by Formula 1 is a line symmetric structure.
9. The organic semiconductor element according to claim 1, wherein the number of carbon atoms in the group represented by Formula W is 5 to 40.
10. The organic semiconductor element according to claim 1, wherein LW is a single bond, a divalent linking group represented by any one of Formulae L-1 to L-4 and Formulae L-13 to L-16, or a divalent linking group obtained by bonding two or more divalent linking groups represented by any one of Formulae L-1 to L-4 and Formulae L-13 to L-16.
11. The organic semiconductor element according to claim 1, wherein LW is a single bond or a divalent linking group represented by any one of Formulae L-1 to L-4 and Formulae L-13 to L-16.
12. The organic semiconductor element according to claim 1, wherein SW is a single bond.
13. The organic semiconductor element according to claim 1, wherein LW is a single bond or a divalent linking group represented by any one of Formula L-1 and Formulae L-13 to L-16.
14. The organic semiconductor element according to claim 1, wherein TW is an alkyl group.
15. The organic semiconductor element according to claim 1, wherein a group represented by Formula W is an alkyl group.
16. A composition for forming an organic semiconductor film, comprising:
a solvent having a boiling point of 100° C. or higher; and
a compound represented by Formula 1,
wherein a content of the compound represented by Formula 1 is from 0.001% by mass to 15% by mass with respect to a total amount of the composition for forming an organic semiconductor film:
Figure US10497881-20191203-C01436
wherein, in Formula 1, X11 and X12 each independently represent a chalcogen atom, Z1a to Z1j each independently represent a hydrogen atom or a halogen atom, A11 represents ═CRA11— or a nitrogen atom, RA11 represents a hydrogen atom or a group represented by R11, A12 represents ═CRA12— or a nitrogen atom, RA12 represents a hydrogen atom or a group represented by R12, n1 represents 0 or 1, p1 represents an integer of 0 to 2 in a case where A11 is ═CRA11— and represents 0 or 1 in a case where A11 is a nitrogen atom, q1 represents an integer of 0 to 2 in a case where A12 is ═CRA12—, and represents 0 or 1 in a case where A12 is a nitrogen atom, R11 and R12 each independently represent a halogen atom, an aryl group, a heteroaryl group, or a group represented by Formula W below:

—SW-LW-TW  (W)
wherein, in Formula W, SW represents a single bond or an alkylene group represented by —(CRS 2)k—, RS each independently represent a hydrogen atom or a halogen atom, k represents an integer of 1 to 17, LW represents a single bond, a divalent linking group represented by any one of Formulae L-1 to L-16 below, or a group obtained by bonding any two or more of divalent linking groups represented by Formulae L-1 to L-16 below, TW represents an alkyl group, a cyano group, a vinyl group, an ethynyl group, an aryl group, a heteroaryl group, an oxyethylene group, an oligooxyethylene group of which the repetition number of oxyethylene units is two or greater, an oligosiloxane group having two or more silicon atoms, or a trialkylsilyl group, and
Figure US10497881-20191203-C01437
Figure US10497881-20191203-C01438
wherein, in Formulae L-1 to L-16, * and wavy line portions represent bonding positions to other structures, p13 represents an integer of 0 to 4, p14, p15, and p16 each independently represent an integer of 0 to 2, RL1, RL21, RL22, RL13, RL14, RL15, and RL16 each independently represent a hydrogen atom or a substituent.
17. The composition for forming an organic semiconductor film according to claim 16, wherein all of Z1a to Z1j are hydrogen atoms.
18. The composition for forming an organic semiconductor film according to claim 16, wherein n1 is 0.
19. The composition for forming an organic semiconductor film according to claim 16, wherein at least one of p1 or q1 is not 0.
20. The composition for forming an organic semiconductor film according to claim 16, wherein:
at least one of p1 or q1 is not 0, and
at least one of R11 or R12 is a group represented by Formula W.
21. The composition for forming an organic semiconductor film according to claim 16, wherein p1 and q1 is 1.
22. The composition for forming an organic semiconductor film according to claim 16, wherein both of X11 and X12 are S atoms, A11 is ═CRA11—, and A12 is ═CRA12—.
23. The composition for forming an organic semiconductor film according to claim 16, wherein the compound represented by Formula 1 is a compound represented by Formula 2 below:
Figure US10497881-20191203-C01439
wherein, in Formula 2, X21 and X22 each independently represent a chalcogen atom, W21 and W22 each independently represent a group represented by Formula W.
24. The composition for forming an organic semiconductor film according to claim 16, wherein the compound represented by Formula 1 is a line symmetric structure.
25. The composition for forming an organic semiconductor film according to claim 16, wherein the number of carbon atoms in the group represented by Formula W is 5 to 40.
26. The composition for forming an organic semiconductor film according to claim 16, wherein LW is a single bond, a divalent linking group represented by any one of Formulae L-1 to L-4 and Formulae L-13 to L-16, and a divalent linking group obtained by bonding two or more divalent linking groups represented by any one of Formulae L-1 to L-4 and Formulae L-13 to L-16.
27. The composition for forming an organic semiconductor film according to claim 16, wherein LW is a single bond or a divalent linking group represented by any one of Formulae L-1 to L-4 and Formulae L-13 to L-16.
28. The composition for forming an organic semiconductor film according to claim 16, wherein SW is a single bond.
29. The composition for forming an organic semiconductor film according to claim 16, wherein LW is a single bond or a divalent linking group represented by any one of Formula L-1 and Formulae L-13 to L-16.
30. The composition for forming an organic semiconductor film according to claim 16, wherein TW is an alkyl group.
31. The composition for forming an organic semiconductor film according to claim 16, wherein a group represented by Formula W is an alkyl group.
32. The composition for forming an organic semiconductor film according to claim 16, further comprising:
a binder polymer,
wherein a content of the binder polymer is 10 mass % or less with respect to a total amount of the composition for forming an organic semiconductor film.
33. A compound represented by Formula 1 below:
Figure US10497881-20191203-C01440
wherein, in Formula 1, X11 and X12 each independently represent a chalcogen atom, Z1a to Z1j each independently represent a hydrogen atom or a halogen atom, A11 represents ═CRA11— or a nitrogen atom, RA11 represents a hydrogen atom or a group represented by R11, A12 represents ═CRA12— or a nitrogen atom, RA12 represents a hydrogen atom or a group represented by R12, n1 represents 0 or 1, p1 represents an integer of 0 to 2 in a case where A11 is ═CRA11— and represents 0 or 1 in a case where A11 is a nitrogen atom, q1 represents an integer of 0 to 2 in a case where A12 is ═CRA12— and represents 0 or 1 in a case where A12 is a nitrogen atom, at least one of p1 or q1 is not 0, R11 and R12 each independently represent a halogen atom, an aryl group, a heteroaryl group, or a group represented by Formula W below:

—SW-LW-TW  (W)
wherein, in Formula W, SW represents a single bond or an alkylene group represented by —(CRS 2)k—, RS each independently represent a hydrogen atom or a halogen atom, k represents an integer of 1 to 17, LW represents a single bond, a divalent linking group represented by any one of Formulae L-1 to L-16 below, or a group obtained by bonding any two or more of divalent linking groups represented by Formulae L-1 to L-16 below, TW represents an alkyl group, a cyano group, a vinyl group, an ethynyl group, an aryl group, a heteroaryl group, an oxyethylene group, an oligooxyethylene group of which the repetition number of oxyethylene units is two or greater, an oligosiloxane group having two or more silicon atoms, or a trialkylsilyl group, and
Figure US10497881-20191203-C01441
Figure US10497881-20191203-C01442
wherein, in Formulae L-1 to L-16, * and wavy line portions represent bonding positions to other structures, p13 represents an integer of 0 to 4, p14, p15, and p16 each independently represent an integer of 0 to 2, RL1, RL21, RL22, RL13, RL14, RL15, and RL16 each independently represent a hydrogen atom or a substituent.
34. A method of manufacturing an organic semiconductor film, comprising:
an applying step of applying the composition for forming an organic semiconductor film according to claim 16 to a substrate, and
a removing step of removing at least a portion of the solvent having a boiling point of 100° C. or higher included in the composition for forming an organic semiconductor film.
35. The method of manufacturing the organic semiconductor film according to claim 34, wherein the applying step is performed by an ink jet method or a flexographic printing method.
36. An organic semiconductor film comprising the compound according to claim 33.
37. A method of manufacturing an organic semiconductor element, comprising:
an applying step of applying the composition for forming an organic semiconductor film according to claim 16 to a substrate, and
a removing step of removing at least a portion of the solvent having a boiling point of 100° C. or higher included in the composition for forming an organic semiconductor film.
38. The method of manufacturing the organic semiconductor element according to claim 37, wherein the applying step is performed by an ink jet method or a flexographic printing method.
39. An organic semiconductor element comprising the compound according to claim 33.
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